Printable Composition for an Ionic Gel Separation Layer For Energy Storage Devices

ABSTRACT

Representative embodiments provide a composition for printing a liquid or gel separator utilized to separate and space apart first and second conductors or electrodes of an energy storage device, such as a battery or a supercapacitor. A representative composition comprises a plurality of particles, typically having a size (in any dimension) between about 0.5 to about 50 microns; a first, ionic liquid electrolyte; and a polymer or polymeric precursor. In another representative embodiment, the plurality of particles comprise diatoms, diatomaceous frustules, and/or diatomaceous fragments or remains. Another representative embodiment further comprises a second electrolyte different from the first electrolyte; the plurality of particles are comprised of silicate glass; the first and second electrolytes comprise zinc tetrafluoroborate salt in 1-ethyl-3-methylimidalzolium tetrafluoroborate ionic liquid; and the polymer comprises polyvinyl alcohol (“PVA”) or polyvinylidene fluoride (“PVFD”). Additional components, such as additional electrolytes and solvents, may also be included.

CROSS-REFERENCE TO A RELATED APPLICATION

This application is a continuation of and claims priority to and thebenefit of U.S. patent application Ser. No. 14/831,659, filed Aug. 10,2015, inventors Vera Nicholaevna Lockett et al., titled “PrintableComposition for an Ionic Gel Separation Layer For Energy StorageDevices”, which is a continuation of and claims priority to and thebenefit of U.S. patent application Ser. No. 13/571,302, filed Aug. 9,2012, inventors Vera Nicholaevna Lockett et al., titled “PrintableComposition for an Ionic Gel Separation Layer For Energy StorageDevices”, which is a nonprovisional of and claims priority to and thebenefit of U.S. Provisional Patent Application Ser. No. 61/672,062,filed Jul. 16, 2012, inventor Vera Nicholaevna Lockett, entitled“Printable Ionic Gel Separation Layer For Energy Storage Devices”, whichis commonly assigned herewith, the entire contents of which areincorporated herein by reference with the same full force and effect asif set forth in their entirety herein, and with priority claimed for allcommonly disclosed subject matter.

FIELD OF THE INVENTION

The present invention in general is related to energy storage technologyand, in particular, is related to separators between electrodes forenergy storage devices such as supercapacitors and batteries, and moreparticularly, is related to printable gel separation layers havingembedded structural components.

BACKGROUND OF THE INVENTION

Various discrete electrode separators or separation layers for energystorage devices are known. For example, typical separators often consistof a separate porous membrane or sheet which is subsequently(post-fabrication) soaked in an electrolyte and then individually placedand laminated in between two electrodes and the other compositionsutilized in the particular device, such as a lithium ion battery. Such aplacement and lamination process, however, limits manufacturingthroughput and is comparatively expensive. In addition, such laminationprocesses are not amenable to creating an energy storage device having asubstantially flat form factor, and instead typically create a bubble,blister or pillow-shaped device, especially when volatile electrolytesare used and, as a result, are unable to create a series of energystorage cells stably stacked one on top of the other.

Various gelatinous (“gel”) separators are also known but are notamenable for use in a printing process. For example, the known gelseparators have insufficient structural strength and cannot withstandthe physical forces applied during a printing process such as screenprinting, resulting in insufficient electrode separation and electricalshorting of the electrodes.

Other known separation techniques have included the provision ofembedded separators within the electrodes themselves. Such electrodes,however, must be formed as separate sheets and a lamination or otherassembly process also must be utilized for device fabrication, againbeing comparatively expensive and limiting throughput, as the forcesgenerated in any type of printing process would also result ininsufficient electrode separation and electrical shorting of theelectrodes.

As a result, a need remains for a liquid or gel separator utilized toseparate and space apart first and second electrodes of an energystorage device, such as a battery or a supercapacitor, and which isformed from a composition that is capable of being printed on a widevariety of surfaces, including irregular, uneven or otherwise non-smoothsurfaces, for example and without limitation. A resulting separator alsomay be flexible and capable of being printed or otherwise applied in awide variety of configurations, shapes, and form factors. Such aseparator should also be comparatively thin to minimize or diminishresistivity or other impedance and have a comparatively high ionicconductivity. In addition, a resulting separator should have sufficientstructural strength and integrity to allow and facilitate the printingof additional layers, such as additional electrodes and interveningenergy storage materials and compositions.

SUMMARY

The exemplary or representative embodiments have a structure differentfrom the structures of previously known electrode or conductorseparators. Representative embodiments provide a liquid or gel separatorutilized to separate and space apart first and second conductors orelectrodes of an energy storage device, such as a battery or asupercapacitor, and compositions therefor.

A representative embodiment of a printable composition to form a liquidor gel separator used for separating and spacing apart at least twoconductors or electrodes, such as an anode and cathode, with the liquidor gel separator printable composition (also referred to as an “ink”)comprising: a plurality of particles; an ionic liquid electrolyte; and apolymer or polymeric precursor. Such a composition may further compriseadditional electrolytes, and further comprise any of various solvents orviscosity modifiers, which may or may not remain in the resulting liquidor gel separator.

Another representative embodiment provides a liquid or gel separatorused for separating and spacing apart at least two conductors,electrodes or current collectors (and any intervening layers), with theliquid or gel separator comprising: a plurality of particles; an ionicliquid electrolyte; and a polymer. Such a liquid or gel separator mayfurther comprise additional electrolytes and possibly trace amounts anyof various solvents or viscosity modifiers utilized in the printable(ink) composition. Alternatively, depending upon the selectedembodiment, such a liquid or gel separator may further comprise suchsolvents, viscosity modifiers or other compounds and compositionsselected to remain in the resulting liquid or gel separator at levelshigher than trace amounts.

In a representative embodiment, the plurality of particles aremicroparticles and have a size (in any dimension) between about 0.5 toabout 50 microns, or more particularly between about 0.5 to about 30microns, or more particularly between about 2.0 to about 20 microns, ormore particularly between about 4.0 to about 15 microns, or moreparticularly between about 5.0 to about 15 microns, or more particularlybetween about 5.0 to about 10 microns, or more particularly betweenabout 6.0 to about 8.0 microns.

Also in a representative embodiment, for any selected particle size,there may be a comparatively narrow distribution or variance of diametersizes, such as for a substantially spherical particle, to facilitatecomparatively dense packing of the particles in a liquid or gelseparator. For example, for a 10 micron selected particle size, it maybe advantageous for the particles to be within a 2 micron variance,e.g., 10 μ±2 μ, and multiple comparatively narrow ranges are also withinthe scope of the disclosure, such as 7 μ±2 μ, 10 μ±1.5 μ, 15 μ±3 μ, 12μ±1.5 μ, and so on.

In another representative embodiment, the particles are packed in one ormore layers, generally to be touching or abutting any adjacent particlesand, when not abutting, to be within a distance of about a one particlediameter from its neighbors. In an exemplary embodiment, the pluralityof particles are substantially spherical and densely packed in amonolayer, or a bilayer, or something in between (e.g., two or fewerlayers), to provide a liquid or gel separator having a thickness of 1-2particle diameters, e.g., a thickness of 1.5 particle diameters. Inother exemplary embodiments, additional particle layers may also beutilized.

In another representative embodiment, the plurality of particles areselected from the group consisting of: diatoms, diatomaceous frustules,diatomaceous fragments, diatomaceous remains, and mixtures thereof. Forsuch an exemplary embodiment, the plurality of particles have a size (inany dimension) between about 0.5 to about 200 microns, or moreparticularly between about 2.0 to about 100 microns, or moreparticularly between about 2.0 to about 50 microns, or more particularlybetween about 4.0 to about 30 microns, or more particularly betweenabout 5.0 to about 30 microns. For example and without limitation, arepresentative diatom, diatomaceous frustule, diatomaceous fragment orother diatomaceous remains may have a size on the order of about 5microns in diameter and about 20-30 microns in length.

The ionic liquid electrolyte, in a representative embodiment, comprisesa combination of one or more types of ionic liquid cations and/or one ormore types of ionic liquid anions, and there may be a wide variety ofany such combinations of ionic liquid anions and/or cations. Inaddition, any selected ionic liquid cation or ionic liquid anion may bepaired with any other type of ion (anion or cation respectively) whichis not an ionic liquid electrolyte, including any another type of anionor cation, such as a salt dissolved in water or another solvent or asalt of an ionic liquid, e.g., lithiumbis(trifluoromethylsulfonyl)imide, also for example and withoutlimitation. For example and without limitation, a selected ionic liquidelectrolyte combination may include an ionic liquid cation, an ionicliquid anion, a selected salt and a solvent. Also for example andwithout limitation, a selected ionic liquid electrolyte combination mayinclude an ionic liquid cation or anion and an anion or cation which isnot an ionic liquid, such as lithium bis(trifluoromethylsulfonyl)imidementioned above.

In a representative embodiment, for example and without limitation, arepresentative ionic liquid cation may be selected from the groupconsisting of: butyltrimethylammonium, 1-ethyl-3-methylimidazolium,1-butyl-3-methylimidazolium, 1-methyl-3-propylimidazolium,1-hexyl-3-methylimidazolium, choline, ethylammonium,tributylmethylphosphonium, tributyl(tetradecyl)phosphonium,trihexyl(tetradecyl)phosphonium, 1-ethyl-2,3-methylimidazolium,1-butyl-1-methylpiperidinium, diethylmethylsulfonium ,1-methyl-3-propylimidazolium, 1-methyl-1-propylpiperidinium,1-butyl-2-methylpyridinium, 1-butyl-4-methylpyridinium,1-butyl-1-methylpyrrolidinium, and mixtures thereof.

Also for example and without limitation, a representative ionic liquidanion or other type of anion may be selected from the group consistingof: tris(pentafluoroethyl)trifluorophosphate, trifluoromethanesulfonate,hexafluorophosphate, tetrafluoroborate, ethyl sulfate, methyl sulfate,dimethyl phosphate, trifluoromethanesulfonate, methanesulfonate,triflate, tricyanomethanide, dibutylphosphate,bis(trifluoromethylsulfonyl)imide, bis-2,4,4-(trimethylpentyl)phosphinate, iodide, chloride, bromide, nitrate, thiocyanate, andmixtures thereof.

Continuing with the examples, a representative combination of ionicliquid electrolytes (anions and cations) and other electrolytecompositions, in a representative embodiment, comprises one or moreionic liquid electrolyte anions, cations and/or other compounds, salts,mixtures, or other anions or cations, for example and withoutlimitation, and may be selected from the group consisting of:butyltrimethylammonium bis(trifluoromethylsulfonyl)imide,1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide,1-methyl-3-propylimidazolium bis(trifluoromethylsulfonyl)imide,1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, cholinebis(trifluoromethylsulfonyl)imide, ethylammonium nitrate,tributylmethylphosphonium methylsulfate, 1-ethyl-2,3-methylimidazoliumtetrafluoroborate, 1-butyl-1-methylpiperidinium iodide,diethylmethylsulfonium bis(trifluoromethylsulfonyl)imide,1-methyl-3-propylimidazolium iodide, 1-ethyl-3-methylimidazoliumthiocyanate, 1-methyl-1-propylpiperidiniumbis(trifluoromethylsulfonyl)imide, 1-butyl-2-methylpyridiniumbis(trifluoromethylsulfonyl)imide, 1-butyl-4-methylpyridiniumbis(trifluoromethylsulfonyl)imide, 1-butyl-1-methylpyrrolidiniumbis(trifluoromethylsulfonyl)imide, diethylmethylsulfoniumbis(trifluoromethylsulfonyl)imide; including salts, such as metallicsalts such as lithium, zinc, silver, cadmium and nickel of thefollowing: bis(trifluoromethylsulfonyl)imide,tris(pentafluoroethyl)trifluorophosphate, trifluoromethanesulfonate,hexafluorophosphate, tetrafluoroborate, ethyl sulfate, dimethylphosphate, trifluoromethanesulfonate, triflate, tricyanomethanide,dibutylphosphate; and mixtures thereof.

A particular advantage of using such an ionic liquid electrolyte (anionand/or cation) is its very low vapor pressure, resulting generally in alack of evaporation at room temperature, fabrication temperatures andoperating temperatures, which is very different than typical water-basedor solvent-based electrolyte systems.

A representative polymer or polymeric precursor, in a representativeembodiment, comprises one or more polymers selected from the groupconsisting of: polymers (or equivalently, polymeric precursors orpolymerizable precurors) such as polyvinyl pyrrolidone (“PVP”, alsoreferred to or known as polyvinyl pyrrolidinone), polyvinyl alcohol(“PVA”), polyvinylidene fluoride (“PVFD”), polyvynylidenefluoride-trifluoroethylene, polytetrafluoroethylene (“PTFE”),polydimethylsiloxane, polyethelene, polypropylene, polyethylene oxide,polypropylene oxide, polyethylene glycolhexafluoropropylene,polyethylene terefphtalatpolyacrylonitryle, polyvinylalcogel,polyvinylpyrrolidone, polyvynilchloride, polyvinyl butyral; polyimidepolymers and copolymers (including aliphatic, aromatic and semi-aromaticpolyimides) such as polyamide, polyaramides, polyacrylamide; acrylateand (meth)acrylate polymers and copolymers such aspolymethylmethacrylate, polyacrylonitrile, acrylonitrile butadienestyrene, allylmethacrylate, polyvinylcaprolactam, polystyrene,polybutadiene, polybutylene terephthalate, polycarbonate,polychloroprene, polyethersulfone, nylon, styrene-acrylonitrile resin;clays such as hectorite clays, garamite clays, organo-modified clays;saccharides and polysaccharides such as guar gum, xanthan gum, starch,butyl rubber, agarose, pectin; celluloses and modified celluloses suchas hydroxy methylcellulose, methylcellulose, ethyl cellulose, propylmethylcellulose, methoxy cellulose, methoxy methylcellulose, methoxypropyl methylcellulose, hydroxy propyl methylcellulose, carboxymethylcellulose, hydroxy ethylcellulose, ethyl hydroxyl ethylcellulose,cellulose ether, cellulose ethyl ether, chitosan; fumed silica, silicapowders and modified ureas; and mixtures thereof.

A representative liquid or gel separator printable composition (or ink)may further comprise a solvent. In a representative embodiment, thesolvent comprises one or more solvents selected from the groupconsisting of: water; alcohols such as methanol, ethanol, N-propanol(including 1-propanol, 2-propanol (isopropanol or IPA),1-methoxy-2-propanol), butanol (including 1-butanol, 2-butanol(isobutanol)), pentanol (including 1-pentanol, 2-pentanol, 3-pentanol),hexanol (including 1-hexanol, 2-hexanol, 3-hexanol), octanol, N-octanol(including 1-octanol, 2-octanol, 3-octanol), tetrahydrofurfuryl alcohol(THFA), cyclohexanol, cyclopentanol, terpineol; lactones such as butyllactone; ethers such as methyl ethyl ether, diethyl ether, ethyl propylether, and polyethers; ketones, including diketones and cyclic ketones,such as cyclohexanone, cyclopentanone, cycloheptanone, cyclooctanone,acetone, benzophenone, acetylacetone, acetophenone, cyclopropanone,isophorone, methyl ethyl ketone; esters such ethyl acetate, dimethyladipate, proplyene glycol monomethyl ether acetate, dimethyl glutarate,dimethyl succinate, glycerin acetate, carboxylates; glycols such asethylene glycols, diethylene glycols, polyethylene glycols, propyleneglycols, dipropylene glycols, glycol ethers, glycol ether acetates;carbonates such as propylene carbonate; glycerols and other polyols andpolymeric polyols or glycols such as glycerin, diol, triol, tetraol,pentaol, ethylene glycol, 1,4-butanediol, 1,2-butanediol,2,3-butanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol,1,8-octanediol, 1,2-propanediol, 1,3-butanediol, 1,2-pentanediol,etohexadiol, p-menthane-3,8-diol, 2-methyl-2,4-pentanediol; tetramethylurea, n-methylpyrrolidone, acetonitrile, tetrahydrofuran (THF), dimethylformamide (DMF), N-methyl formamide (NMF), dimethyl sulfoxide (DMSO);thionyl chloride; sulfuryl chloride; and mixtures thereof. Any of thesevarious solvents may also further comprise an acid or a base (liquid ordissolved solid), such as to adjust overall pH (or pK) or influenceanother property, including inorganic and/or organic acids such ascarboxylic acids (including dicarboxylic acids, tricarboxylic acids,alkyl carboxylic acids, and so on, e.g., dicarboxylic acids such aspropanedioic (malonic) acid, butanedioic (succinic) acid, pentanedioic(glutaric) acid, hexanedioic (adipic) acid, heptanedioic (pimelic) acid,octanedioic (suberic) acid, nonanedioic (azelaic) acid, decanedioic(sebacic) acid, undecanedioic acid, dodecanedioic acid, tridecanedioic(brassylic) acid, tetradecanedioic acid, pentadecanedioic acid,hexadecanedioic (thapsic) acid, octadecanedioic acid); acetic acid;oxalic acid; mellitic acid; formic acid, chloroacetic acid; benzoicacid; trifluoroacetic acid; propanoic acid; butanoic acid; hydrochloricacid; sulfuric acid; carbonic acid; and bases such as ammoniumhydroxide, sodium hydroxide, potassium hydroxide; and mixtures thereof.

The plurality of particles, in a representative embodiment, comprise oneor more particles selected from the group consisting of: glass, alumina,polystyrene, melamine, and mixtures thereof. The plurality of particles,in another representative embodiment, comprise diatoms, diatomaceousfrustules, and/or diatomaceous fragments or remains. The plurality ofparticles, in another representative embodiment, comprise in a cured orsolidified form one or more particles selected from the group consistingof: polymers (or equivalently, polymeric precursors or polymerizableprecurors) such as polyvinyl pyrrolidone (“PVP”, also referred to orknown as polyvinyl pyrrolidinone), polyvinyl alcohol (“PVA”),polyvinylidene fluoride (“PVFD”), polyvynylidenefluoride-trifluoroethylene, polytetrafluoroethylene (“PTFE”),polydimethylsiloxane, polyethelene, polypropylene, polyethylene oxide,polypropylene oxide, polyethylene glycolhexafluoropropylene,polyethylene terefphtalatpolyacrylonitryle, polyvinylalcogel,polyvinylpyrrolidone, polyvynilchloride, polyvinyl butyral; polyimidepolymers and copolymers (including aliphatic, aromatic and semi-aromaticpolyimides) such as polyamide, polyaramides, polyacrylamide; acrylateand (meth)acrylate polymers and copolymers such aspolymethylmethacrylate, polyacrylonitrile, acrylonitrile butadienestyrene, allylmethacrylate, polyvinylcaprolactam, polystyrene,polybutadiene, polybutylene terephthalate, polycarbonate,polychloroprene, polyethersulfone, nylon, styrene-acrylonitrile resin;clays such as hectorite clays, garamite clays, organo-modified clays;saccharides and polysaccharides such as guar gum, xanthan gum, starch,butyl rubber, agarose, pectin; celluloses and modified celluloses suchas hydroxy methylcellulose, methylcellulose, ethyl cellulose, propylmethylcellulose, methoxy cellulose, methoxy methylcellulose, methoxypropyl methylcellulose, hydroxy propyl methylcellulose, carboxymethylcellulose, hydroxy ethylcellulose, ethyl hydroxyl ethylcellulose,cellulose ether, cellulose ethyl ether, chitosan; fumed silica, silicapowders and modified ureas; and mixtures thereof.

A representative liquid or gel separator printable composition (or ink)and a resulting representative liquid or gel separator may furthercomprise an additional, second electrolyte different from the firstelectrolyte, such as an acid, a base, a salt dissolved in a solvent(e.g., water, an organic solvent), or a salt dissolvable or miscible inan ionic liquid, to form free ions. In a representative embodiment, asecond electrolyte comprises one or more electrolytes selected from thegroup consisting of: potassium hydroxide, sodium hydroxide, ammoniumhydroxide, lithium hydroxide, nickel hydroxide, cadmium hydroxide,magnesium hydroxide, sulfuric acid, hydrochloric acid, fluoroboric acid,ammonium chloride, zinc chloride, zincbis(trifluoromethanesulfonyl)imide, aluminium chloride, chromiumchloride, magnesium perchloride, barium chromate, lithium chromate,lithium-thyonyl chloride, lithiujm perchlorate, lithium bromide, lithiumtriflate, lithium hexafluorophosphate, lithium tetrafluoroborate,lithium bis-oxalato borate, lithium bis(trifluoromethanesulfonyl)imide,lithium bisoxalatoborate, lithium iodide, lithium tetrachloroaluminate,potassium carbonate, potassium fluoride, potassium borate, silvernitride, silver tetrafluoroborate; and mixtures thereof.

Another representative embodiment provides a liquid or gel separator forseparating and spacing apart at least two conductors, the liquid or gelseparator comprising: a plurality of particles having a size (in anydimension) between about 0.5 to about 30 microns, wherein the pluralityof particles comprise one or more particles selected from the groupconsisting of: silicate glass, silicon dioxide, alumina, polystyrene,melamine, diatoms, diatomaceous frustules, diatomaceous fragments,diatomaceous remains; and mixtures thereof; a first, ionic liquidelectrolyte; and a polymer.

Another representative embodiment provides a liquid or gel separator forseparating and spacing apart at least two conductors, the liquid or gelseparator comprising: a plurality of particles; a first, ionic liquidelectrolyte; a second electrolyte different from the first electrolyte;and a polymer.

Another representative embodiment provides a liquid or gel separator forseparating and spacing apart at least two conductors, the liquid or gelseparator comprising: a plurality of substantially spherical particlescomprised of silicate glass and having a diameter between about 5.0 toabout 15 microns, wherein each substantially spherical particle of theplurality of substantially spherical particles is abutting or withinabout one diameter of adjacent substantially spherical particles of theplurality of substantially spherical particles; a first electrolyte; anda polymer.

Yet another representative embodiment provides a liquid or gel separatorfor separating and spacing apart at least two conductors, the liquid orgel separator comprising: a plurality of particles having a size (in anydimension) between about 3.0 to about 15 microns and present in anamount between about 40%-75% by weight, wherein the plurality ofparticles comprise one or more particles selected from the groupconsisting of: silicate glass, silicon dioxide, alumina, polystyrene,melamine, diatoms, diatomaceous frustules, diatomaceous fragments,diatomaceous remains; and mixtures thereof; a first, ionic liquidelectrolyte; a second electrolyte different from the first electrolyte,wherein the first and second electrolytes comprise zinctetrafluoroborate salt in 1-ethyl-3-methylimidalzolium tetrafluoroborateionic liquid and are present in an amount between about 15%-45% byweight; and a polymer comprising polyvinyl alcohol (“PVA”) orpolyvinylidene fluoride (“PVFD”) or mixtures thereof and present in anamount between about 0.5%-15% by weight.

Another representative embodiment provides a printable compositioncomprising: a plurality of particles; a first, ionic liquid electrolyte;and a polymer or polymeric precursor.

Another representative embodiment provides a printable compositioncomprising: a plurality of particles having a size (in any dimension)between about 0.5 to about 30 microns, wherein the plurality ofparticles comprise one or more particles selected from the groupconsisting of: silicate glass, silicon dioxide, alumina, polystyrene,melamine, diatoms, diatomaceous frustules, diatomaceous fragments,diatomaceous remains; and mixtures thereof; a first, ionic liquidelectrolyte; and a polymer or polymeric precursor.

Another representative embodiment provides a printable compositioncomprising: a plurality of particles; a first, ionic liquid electrolyte;a second electrolyte different from the first electrolyte; and a polymeror polymeric precursor.

Yet another representative embodiment provides a printable compositioncomprising: a plurality of particles having a size (in any dimension)between about 3.0 to about 15 microns and present in an amount betweenabout 40%-75% by weight, wherein the plurality of particles comprise oneor more particles selected from the group consisting of: silicate glass,silicon dioxide, alumina, polystyrene, melamine, diatoms, diatomaceousfrustules, diatomaceous fragments, diatomaceous remains; and mixturesthereof; a first, ionic liquid electrolyte; a second electrolytedifferent from the first electrolyte, wherein the first and secondelectrolytes comprise zinc tetrafluoroborate salt in1-ethyl-3-methylimidalzolium tetrafluoroborate ionic liquid and arepresent in an amount between about 15%-45% by weight; a polymer orpolymeric precursor comprising polyvinyl alcohol (“PVA”) orpolyvinylidene fluoride (“PVFD”) or mixtures thereof and present in anamount between about 0.5%-15% by weight; and a solvent comprisingN-methyl-2-pyrrolidinone present in an amount between about 15%-25% byweight.

Another representative embodiment provides a composition comprising: aplurality of particles having a size (in any dimension) between about0.5 to about 50 microns; an ionic liquid electrolyte; and a polymer orpolymeric precursor. Another representative embodiment provides acomposition comprising: a plurality of particles selected from the groupconsisting of: diatoms, diatomaceous frustules, diatomaceous fragments,diatomaceous remains, and mixtures thereof; an ionic liquid electrolyte;and a polymer or polymeric precursor. A method of using suchcompositions is also disclosed, the method comprising: printing thecomposition to form a liquid or gel separator.

In addition, another representative embodiment provides a liquid or gelseparator for separating and spacing apart at least two conductors, theliquid or gel separator comprising: a plurality of particles selectedfrom the group consisting of: diatoms, diatomaceous frustules,diatomaceous fragments, diatomaceous remains, and mixtures thereof; afirst, ionic liquid electrolyte; and a polymer.

Another representative embodiment provides a liquid or gel separator forseparating and spacing apart at least two conductors, the liquid or gelseparator comprising: a plurality of particles selected from the groupconsisting of: diatoms, diatomaceous frustules, diatomaceous fragments,diatomaceous remains, and mixtures thereof; a first, ionic liquidelectrolyte; a second electrolyte different from the first electrolyte;and a polymer.

Another representative embodiment provides a composition comprising: aplurality of particles selected from the group consisting of: diatoms,diatomaceous frustules, diatomaceous fragments, diatomaceous remains,and mixtures thereof; a first, ionic liquid electrolyte; and a polymeror polymeric precursor.

Another representative embodiment provides a composition comprising: aplurality of particles selected from the group consisting of: diatoms,diatomaceous frustules, diatomaceous fragments, diatomaceous remains,and mixtures thereof; a first, ionic liquid electrolyte; a secondelectrolyte different from the first electrolyte; and a polymer orpolymeric precursor.

Yet another representative embodiment provides a composition comprising:a plurality of particles having a size (in any dimension) between about0.5 to about 200 microns and present in an amount between about 40%-75%by weight, wherein the plurality of particles comprise one or moreparticles selected from the group consisting of: diatoms, diatomaceousfrustules, diatomaceous fragments, diatomaceous remains, and mixturesthereof; a first, ionic liquid electrolyte; a second electrolytedifferent from the first electrolyte, wherein the first and secondelectrolytes comprise zinc tetrafluoroborate salt in1-ethyl-3-methylimidalzolium tetrafluoroborate ionic liquid and arepresent in an amount between about 15%-45% by weight; a polymer orpolymeric precursor comprising polyvinyl alcohol (“PVA”) orpolyvinylidene fluoride (“PVFD”) or mixtures thereof and present in anamount between about 0.5%-15% by weight; and a solvent comprisingN-methyl-2-pyrrolidinone present in an amount between about 15%-25% byweight.

Another representative embodiment provides an energy storage devicecomprising: a first electrode; a second electrode; and a liquid or gelseparator coupled between the first electrode and the second electrode,the liquid or gel separator comprising: a plurality of particles havinga size (in any dimension) between about 0.5 to about 30 microns; anionic liquid electrolyte; and a polymer.

Another representative embodiment provides an energy storage devicecomprising: a first electrode; a second electrode; and a liquid or gelseparator coupled between the first electrode and the second electrode,the liquid or gel separator comprising: a plurality of particlesselected from the group consisting of: diatoms, diatomaceous frustules,diatomaceous fragments, diatomaceous remains, and mixtures thereof; anionic liquid or other electrolyte; and a polymer.

Numerous other advantages and features of the present invention willbecome readily apparent from the following detailed description of theinvention and the embodiments thereof, from the claims and from theaccompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

The objects, features and advantages of the present invention will bemore readily appreciated upon reference to the following disclosure whenconsidered in conjunction with the accompanying drawings, wherein likereference numerals are used to identify identical components in thevarious views, and wherein reference numerals with alphabetic charactersare utilized to identify additional types, instantiations or variationsof a selected component embodiment in the various views, in which:

FIG. 1 is a perspective view illustrating a representative energystorage device embodiment in accordance with the teachings of thepresent disclosure.

FIG. 2 is a cross-sectional view illustrating a first representativeenergy storage device embodiment in accordance with the teachings of thepresent disclosure.

FIG. 3 is a cross-sectional view illustrating a second representativeenergy storage device embodiment in accordance with the teachings of thepresent disclosure.

DETAILED DESCRIPTION OF REPRESENTATIVE EMBODIMENTS

While the present disclosure is susceptible of embodiment in manydifferent forms, there are shown in the drawings and will be describedherein in detail specific exemplary or representative embodimentsthereof, with the understanding that the present description is to beconsidered as an exemplification of the principles of the disclosure andis not intended to limit the invention or the disclosure to the specificembodiments illustrated. In this respect, before explaining at least oneembodiment consistent with the present disclosure in detail, it is to beunderstood that the disclosure is not limited in its application to thedetails of construction and to the arrangements of components set forthabove and below, illustrated in the drawings, or as described in theexamples. Methods and apparatuses consistent with the present disclosureare capable of other embodiments and of being practiced and carried outin various ways. Also, it is to be understood that the phraseology andterminology employed herein, as well as the abstract included below, arefor the purposes of description and should not be regarded as limiting.

FIG. 1 is a perspective view illustrating representative energy storagedevice 100, 101 embodiments in accordance with the teachings of thepresent disclosure, such as a supercapacitor or a battery. FIG. 2 is across-sectional view (through the 20-20′ plane of FIG. 1) illustrating afirst representative energy storage device 100 embodiment, such as asupercapacitor, in accordance with the teachings of the presentdisclosure. FIG. 3 is a cross-sectional view (through the 20-20′ planeof FIG. 1) illustrating a second representative energy storage device101 embodiment, such as a battery, in accordance with the teachings ofthe present disclosure. For example and without limitation, such anenergy storage device 100, 101 may be a supercapacitor or a battery oranother energy storage device, such as any of the representativesupercapacitors disclosed in U.S. patent application Ser. No.13/025,137, filed Feb. 10, 2011, entitled “Multilayer Carbon NanotubeCapacitor” (the “first related patent application”), the entire contentsof which are incorporated herein by reference with the same full forceand effect as if set forth in their entirety herein, and with priorityclaimed for all commonly disclosed subject matter. As illustrated, sucha representative energy storage device 100, 101 is sealed orencapsulated with a sealant 35, to both provide electrical insulationand to prevent leakage of internal contents or components, such asliquids (e.g., ionic liquids) and other components such as carbonnanotubes (“CNTs”) (such as single-walled carbon nanotubes (“SWCNTs”)and multi-walled carbon nanotubes (“MWCNTs”)), also for example andwithout limitation. Any type of suitable sealant which is known orbecomes known in the art may be utilized to form sealant 35, such as thevarious polymers discussed below.

Also as illustrated, external leads (or wires) 15, 25 are typicallyprovided for electrical contact with the corresponding first and secondconductors (or conductive layers) 110 (or 110A), 115 (discussed ingreater detail below, and which may also be referred to equivalently asfirst and second electrodes 110 (or 110A), 115 or equivalently as firstand second current collectors 110 (or 110A), 115), depending upon theembodiment (e.g., typically referred to as current collectors in abattery embodiment). The sealant 35 and leads 15, 25 may be provided asknown or becomes known in the electronic arts. A representative energystorage device 100, 101 may be fabricated, stacked and/or wired inparallel or in series, and may perform as a supercapacitor, a battery,or a battery replacement, or as a fixed electrical “buffer” storage fordistributed power systems, for example and without limitation. Arepresentative energy storage device 100, 101 is illustrated as having asubstantially flat form factor for ease of explanation, and those havingskill in the electronic arts will understand that a representativeenergy storage device 100, 101 may have any of various forms,thicknesses, and form factors, such as cubic, rolled, folded, etc., andany and all such shapes and sizes are considered equivalent and withinthe scope of the disclosure. For example and as discussed in greaterdetail below, a representative energy storage device 100, 101 may beformed through a printing process on comparatively large, flexiblesheets of a substrate 105 or on a conductive substrate utilized to formfirst conductor 110A, such that a representative energy storage device100, 101 may also be flexible or foldable (even creasable) and formedinto a wide variety of shapes and form factors for any intended purpose.

The first conductor 110 is illustrated as coupled to a substrate 105. Inany of various exemplary embodiments, the first conductor 110 and thesubstrate 105 may be separate components or may be formed as a combinedor integrated conductive substrate, illustrated as first conductor (orconductive layer) 110A in FIG. 3. For example, a first conductor (orconductive layer) 110 may be printed on a flexible substrate 105, suchas illustrated in FIG. 2, or a first conductor (or conductive layer)110A may be comprised of a conductive substrate, such as an aluminumfoil or sheet (which may or may not have another conductive layerdeposited thereon), forming an integrated or combined first conductor110A as illustrated in FIG. 3. The embodiments 100, 101 differ withrespect to the use of a conductive substrate to form the first conductor110A (versus a separate substrate 105 and first conductor 110). Inaddition, the embodiments 100, 101 of FIGS. 2 and 3 also illustrate, asrepresentative examples, different shapes, packing densities, number oflayers and size distributions for a plurality of particles 155, anddifferent form factors (e.g., thicknesses) for an exemplary liquid orgel separator 200. Except for these differences, the illustratedembodiments 100, 101 are otherwise structurally substantially similar(if not identical) in other respects for either a battery embodiment ora supercapacitor embodiment, it being understood, of course, that abattery or supercapacitor generally will have differing compositionscomprising each such layer illustrated, as discussed in greater detailbelow. (Not separately illustrated, depending upon the order offabrication of the various layers and the method of fabrication, thesecond conductor 115 also may be formed as a combined or integratedconductive substrate.)

Layers 120 and 125 comprise any desired chemical composition,electrochemical composition or any other composition suitable for energystorage, such as a composition of CNTs and ionic liquid electrolytes fora supercapacitor as disclosed in the first related patent application,and depending upon the embodiment, may form anode and cathode layers. Inanother representative or exemplary embodiment, such as for a battery,the layers 120 and 125 may comprise zinc-carbon or zinc-silver oxide,for example and without limitation, forming an anode and a cathode, asdescribed in greater detail below. Depending upon the selectedembodiment, the first conductor 110, 110A alone, layer 120 alone, or thefirst conductor 110, 110A coupled with layer 120, may be considered afirst electrode (e.g., an anode), and correspondingly the secondconductor 115 alone, layer 125 alone, or the second conductor 115coupled with layer 125, may be considered a second electrode (e.g., acathode).

The first conductor 110, 110A and layer 120 (e.g., anode) are separatedfrom the second electrode 115 and layer 125 (e.g., cathode) by a liquidor gel separator 200 formed from an exemplary liquid or gel separatorprintable composition (ink) of the present disclosure. (In various otherexemplary embodiments, it is possible that the compositions which wouldotherwise be utilized to form layers 120, 125 (such as an ionic liquidelectrolyte) may be included within liquid or gel separator 200 and, forsuch embodiments, layers 120, 125 may be omitted as separate or discretecomponents of a representative energy storage device 100, 101.)

In various exemplary embodiments, the first conductor 110, 110A and thesecond conductor 115 may be configured as parallel plates or sheets(prior to further configuration, such as folding or rolling), eachhaving a substantially flat form factor, and may be flexible ornonflexible. In other exemplary embodiments, the first conductor 110,110A and the second conductor 115 may each be fan-folded and may beflexible or nonflexible. A representative energy storage device 100, 101also may have any of various overall, resulting shapes, sizes, and formfactors, such as by further folding or rolling of the opposingelectrodes (with their sandwiched contents, the layers 120, 125 on eachside of the gel separator 200).

For completeness, it should be noted that a representative energystorage device 100, 101 is effectively comprised of two, mirror imagehalves, with one half having the first conductor 110, 110A with layer120 and the other half having the second conductor 115 with layer 125.One such half may be fabricated identically to the first such half, andthen placed (upside down or face down, effectively as a mirror image)over the first such half and additional components (layers 120, 125and/or liquid or gel separator 200), such as by folding or lamination.

In an exemplary embodiment, each of these various layers is printed orotherwise deposited successively, printing or depositing a next layerover the previously printed layers. For example and without limitation,the first conductor 110 may be printed or otherwise deposited oversubstrate 105; layer 120 may be printed or otherwise deposited over thefirst conductor 110 (or 110A); the liquid or gel separator 200 may beprinted or otherwise deposited over layer 120; the layer 125 may beprinted or otherwise deposited over the liquid or gel separator 200; andthe second conductor 115 may be printed or otherwise deposited over thelayer 125. This may be performed in line and without lamination orfolding, which provides for much higher throughput and lower fabricationcosts. This is a significant departure from prior art methods which, ata minimum, require separate placement and/or lamination steps for aseparation membrane.

Depending upon the viscosity and temperature, the liquid or gelseparator 200 may be referred to equivalently as a liquid separator oras a gel separator, and any reference to liquid or gel herein shall beunderstood to mean and include the other. It should also be noted thatall described percentages are based on weight, rather than volume orsome other measure.

Liquid or Gel Separator Printable Composition Example 1

A composition comprising:

a plurality of particles;

an ionic liquid electrolyte; and

a polymer or polymeric precursor.

Liquid or Gel Separator Printable Composition Example 2

A composition comprising:

a plurality of particles;

a first electrolyte comprising an ionic liquid;

a second electrolyte different from the first electrolyte; and

a polymer or polymeric precursor.

Liquid or Gel Separator Printable Composition Example 3

A composition comprising:

a plurality of particles having a size (in any dimension) between about0.5 to about 30 microns;

an ionic liquid electrolyte; and

a polymer or polymeric precursor.

Liquid or Gel Separator Printable Composition Example 4

A composition comprising:

a plurality of particles having a size (in any dimension) between about0.5 to about 30 microns and comprised of silicate glass;

an ionic liquid electrolyte; and

a polymer or polymeric precursor.

Liquid or Gel Separator Printable Composition Example 5

A composition comprising:

a plurality of particles having a size (in any dimension) between about0.5 to about 30 microns and comprised of a first polymer;

an ionic liquid electrolyte; and

a second polymer or polymeric precursor, which may be the same ordifferent from the first polymer.

Liquid or Gel Separator Printable Composition Example 6

A composition comprising:

a plurality of particles selected from the group consisting of: diatoms,diatomaceous frustules, diatomaceous fragments, diatomaceous remains,and mixtures thereof;

an ionic liquid electrolyte; and

a polymer or polymeric precursor.

Liquid or Gel Separator Printable Composition Example 7

A composition comprising:

about 10%-90% of a plurality of particles having a size (in anydimension) between about 0.5 to about 30 microns;

about 1%-90% of an ionic liquid electrolyte; and

about 0.5%-90% of a polymer or polymeric precursor.

Liquid or Gel Separator Printable Composition Example 8

A composition comprising:

about 30%-80% of a plurality of particles having a size (in anydimension) between about 0.5 to about 30 microns;

about 5%-50% of an ionic liquid electrolyte; and

about 1%-20% of a polymer or polymeric precursor.

Liquid or Gel Separator Printable Composition Example 9

A composition comprising:

about 40%-60% of a plurality of particles having a size (in anydimension) between about 0.5 to about 30 microns;

about 15%-30% of an ionic liquid electrolyte; and

about 1%-10% of a polymer or polymeric precursor.

Liquid or Gel Separator Printable Composition Example 10

A composition comprising:

a plurality of particles;

an ionic liquid electrolyte;

a polymer or polymeric precursor; and

a solvent.

Liquid or Gel Separator Printable Composition Example 11

A composition comprising:

a plurality of particles;

a first electrolyte comprising an ionic liquid;

a second electrolyte different from the first electrolyte;

a polymer or polymeric precursor; and

a solvent.

Liquid or Gel Separator Printable Composition Example 12

A composition comprising:

a plurality of particles;

an ionic liquid electrolyte;

a polymer or polymeric precursor; and

a viscosity modifier.

Liquid or Gel Separator Printable Composition Example 13

A composition comprising:

a plurality of substantially spherical particles having a size (in anydimension) between about 5.0 to about 15 microns and comprised ofsilicate glass;

a first, ionic liquid electrolyte; and

a polymer or polymeric precursor.

Liquid or Gel Separator Printable Composition Example 14

A composition comprising:

a plurality of substantially spherical particles having a size (in anydimension) of about 10 μ±2 μ and comprised of silicate glass;

a first, ionic liquid electrolyte; and

a polymer or polymeric precursor.

Liquid or Gel Separator Printable Composition Example 15

A composition comprising:

a plurality of particles having a size (in any dimension) between about5.0 to about 15 microns and comprised of silicate glass;

first and second electrolytes comprising zinc tetrafluoroborate salt in1-ethyl-3-methylimidalzolium tetrafluoroborate ionic liquid;

a polymer or polymeric precursor comprising polyvinyl alcohol (“PVA”) orpolyvinylidene fluoride (“PVFD”); and

a solvent comprising N-methyl-2-pyrrolidinone.

Liquid or Gel Separator Printable Composition Example 16

A composition comprising:

about 40%-60% of a plurality of particles having a size (in anydimension) between about 5.0 to about 15 microns and comprised ofsilicate glass;

about 15%-30% of first and second electrolytes comprising zinctetrafluoroborate salt in 1-ethyl-3-methylimidalzolium tetrafluoroborateionic liquid;

about 0.5%-10% of a polymer or polymeric precursor comprising polyvinylalcohol (“PVA”) or polyvinylidene fluoride (“PVFD”); and

about 10%-30% of a solvent comprising N-methyl-2-pyrrolidinone.

Liquid or Gel Separator Printable Composition Example 17

A composition comprising:

about 50%-55% of a plurality of particles having a size (in anydimension) between about 5.0 to about 15 microns and comprised ofsilicate glass;

about 22%-27% of first and second electrolytes comprising zinctetrafluoroborate salt in 1-ethyl-3-methylimidalzolium tetrafluoroborateionic liquid;

about 1.0%-5.0% of a polymer or polymeric precursor comprising polyvinylalcohol (“PVA”) or polyvinylidene fluoride (“PVFD”); and

about 15%-25% of a solvent comprising N-methyl-2-pyrrolidinone.

Liquid or Gel Separator Printable Composition Example 18

A composition comprising:

about 52%-53% of a plurality of particles having a size (in anydimension) between about 5.0 to about 15 microns and comprised ofsilicate glass;

about 24%-26% of first and second electrolytes comprising zinctetrafluoroborate salt in 1-ethyl-3-methylimidalzolium tetrafluoroborateionic liquid;

about 2.0%-3.5% of a polymer or polymeric precursor comprising polyvinylalcohol (“PVA”) or polyvinylidene fluoride (“PVFD”); and

about 19%-21% of a solvent comprising N-methyl-2-pyrrolidinone.

Referring to the examples and to the Figures, in representative orexemplary embodiments, the liquid or gel separator 200 is typicallyformed using a representative or exemplary liquid or gel separatorprintable composition which has been deposited as a layer over a layer120 (or 125, if deposited in a reverse order), such as through aprinting or other deposition process, as mentioned above and as furtherdescribed below. Following curing or drying of the liquid or gelseparator printable composition, the resulting liquid or gel separator200 comprises a liquid or gel polymeric mixture 175 and particles 150,and in turn, the liquid or gel polymeric mixture 175 comprises an ionicliquid electrolyte and a polymer (e.g., formed from a polymerized orcured polymeric precursor), and optionally may include other componentsas necessary or desirable, such as additional electrolytes or traceamounts of solvents, for example and without limitation.

Liquid or Gel Separator 200 Example 1

A composition comprising:

a plurality of particles;

an ionic liquid electrolyte; and

a polymer.

Liquid or Gel Separator 200 Example 2

A composition comprising:

a plurality of particles;

a first electrolyte comprising an ionic liquid;

a second electrolyte different from the first electrolyte; and

a polymer.

Liquid or Gel Separator 200 Example 3

A composition comprising:

a plurality of particles having a size (in any dimension) between about0.5 to about 30 microns;

an ionic liquid electrolyte; and

a polymer.

Liquid or Gel Separator 200 Example 4

A composition comprising:

a plurality of particles having a size (in any dimension) between about0.5 to about 30 microns and comprised of silicate glass;

an ionic liquid electrolyte; and

a polymer.

Liquid or Gel Separator 200 Example 5

A composition comprising:

a plurality of particles selected from the group consisting of: diatoms,diatomaceous frustules, diatomaceous fragments, diatomaceous remains,and mixtures thereof;

an ionic liquid electrolyte; and

a polymer.

Liquid or Gel Separator 200 Example 6

A composition comprising:

a plurality of particles having a size (in any dimension) between about0.5 to about 30 microns and comprised of a first polymer;

an ionic liquid electrolyte; and

a second polymer, which may be the same or different from the firstpolymer.

Liquid or Gel Separator 200 Example 7

A composition comprising:

a plurality of substantially spherical particles having a size (in anydimension) between about 5.0 to about 15 microns and comprised ofsilicate glass, each substantially spherical particle abutting orseparated by less than about one diameter from another adjacentsubstantially spherical particle of the plurality of substantiallyspherical particles;

a first, ionic liquid electrolyte; and

a polymer.

Liquid or Gel Separator 200 Example 8

A composition comprising:

a plurality of substantially spherical particles having a size (in anydimension) between about 5.0 to about 15 microns and comprised ofsilicate glass, each substantially spherical particle abutting orseparated by less than about one diameter from another adjacentsubstantially spherical particle of the plurality of substantiallyspherical particles, and the plurality of substantially sphericalparticles packed or arranged substantially in a monolayer;

a first, ionic liquid electrolyte; and

a polymer.

Liquid or Gel Separator 200 Example 9

A composition comprising:

a plurality of substantially spherical particles having a size (in anydimension) of about 10 μ±2 μ and comprised of silicate glass, eachsubstantially spherical particle abutting or separated by less thanabout one diameter from another adjacent substantially sphericalparticle of the plurality of substantially spherical particles, and theplurality of substantially spherical particles packed or arrangedsubstantially in a monolayer;

a first, ionic liquid electrolyte; and

a polymer.

Liquid or Gel Separator 200 Example 10

A composition comprising:

a plurality of substantially spherical particles having a size (in anydimension) between about 5.0 to about 15 microns and comprised ofsilicate glass, each substantially spherical particle abutting orseparated by less than about one diameter from another adjacentsubstantially spherical particle of the plurality of substantiallyspherical particles, and the plurality of substantially sphericalparticles packed or arranged substantially in two or fewer layers;

a first, ionic liquid electrolyte; and

a polymer.

Liquid or Gel Separator 200 Example 11

A composition comprising:

about 10%-90% of a plurality of particles having a size (in anydimension) between about 0.5 to about 30 microns;

about 1%-90% of an ionic liquid electrolyte; and

about 0.5%-90% of a polymer.

Liquid or Gel Separator 200 Example 12

A composition comprising:

about 30%-80% of a plurality of particles having a size (in anydimension) between about 0.5 to about 30 microns;

about 5%-50% of an ionic liquid electrolyte; and

about 1%-20% of a polymer.

Liquid or Gel Separator 200 Example 13

A composition comprising:

about 40%-60% of a plurality of particles having a size (in anydimension) between about 0.5 to about 30 microns;

about 15%-30% of an ionic liquid electrolyte; and

about 1%-10% of a polymer.

Liquid or Gel Separator 200 Example 14

A composition comprising:

a plurality of particles;

an ionic liquid electrolyte;

a polymer; and

at least trace amounts of a solvent.

Liquid or Gel Separator 200 Example 15

A composition comprising:

a plurality of particles;

a first electrolyte comprising an ionic liquid;

a second electrolyte different from the first electrolyte;

a polymer; and

at least trace amounts of a solvent.

Liquid or Gel Separator 200 Example 16

A composition comprising:

a plurality of particles;

an ionic liquid electrolyte;

a polymer; and

at least trace amounts of a viscosity modifier.

Liquid or Gel Separator 200 Example 17

A composition comprising:

a plurality of particles having a size (in any dimension) between about5.0 to about 15 microns and comprised of silicate glass;

first and second electrolytes comprising zinc tetrafluoroborate salt in1-ethyl-3-methylimidalzolium tetrafluoroborate ionic liquid; and

a polymer comprising polyvinyl alcohol (“PVA”) or polyvinylidenefluoride (“PVFD”).

Liquid or Gel Separator 200 Example 18

A composition comprising:

about 40%-75% of a plurality of particles having a size (in anydimension) between about 5.0 to about 15 microns and comprised ofsilicate glass;

about 15%-45% of first and second electrolytes comprising zinctetrafluoroborate salt in 1-ethyl-3-methylimidalzolium tetrafluoroborateionic liquid; and

about 0.5%-15% of a polymer comprising polyvinyl alcohol (“PVA”) orpolyvinylidene fluoride (“PVFD”).

Liquid or Gel Separator 200 Example 19

A composition comprising:

a plurality of particles having a size (in any dimension) between about5.0 to about 15 microns and comprised of silicate glass;

first and second electrolytes comprising zinc tetrafluoroborate salt in1-ethyl-3-methylimidalzolium tetrafluoroborate ionic liquid;

a polymer comprising polyvinyl alcohol (“PVA”) or polyvinylidenefluoride (“PVFD”); and

at least trace amounts of a solvent comprising N-methyl-2-pyrrolidinone.

Liquid or Gel Separator 200 Example 20

A composition comprising:

about 40%-75% of a plurality of particles having a size (in anydimension) between about 5.0 to about 15 microns and comprised ofsilicate glass;

about 15%-45% of first and second electrolytes comprising zinctetrafluoroborate salt in 1-ethyl-3-methylimidalzolium tetrafluoroborateionic liquid;

about 0.5%-15% of a polymer comprising polyvinyl alcohol (“PVA”) orpolyvinylidene fluoride (“PVFD”); and

at least trace amounts of a solvent comprising N-methyl-2-pyrrolidinone.

Solid, hollow, open or dense particles 150 may be spherical,substantially spherical, near spherical, or may have other shapes andforms, such as faceted, oblong (elliptical), substantially rectangular,substantially flat, or substantially irregular or aspherical particles,any organic shapes (e.g., any of the various shapes of diatoms,diatomaceous frustules, and/or diatomaceous fragments or remains),cubic, or various prismatic shapes (e.g., trapezoidal, triangular,pyramidal, etc.), and are comprised of any substantially non-conductiveor otherwise electrically insulating materials like glass, alumina,polystyrene, melamine, organic materials, natural materials, etc.Typical or representative sizes of particles 150 are about 0.5 to about50 microns, or more particularly between about 0.5 to about 30 microns,or more particularly between about 2.0 to about 20 microns, or moreparticularly between about 4.0 to about 15 microns, or more particularlybetween about 5.0 to about 15 microns, or more particularly betweenabout 5.0 to about 10 microns, or more particularly between about 6.0 toabout 8.0 microns. In a representative embodiment, silicate glass orplastic spheres are utilized to form particles 150, such as aborosilicate glass or other silicate glass, or a plastic or otherpolymer such as polystyrene latex, although any of myriad types ofmaterials may be utilized, including without limitation, other types ofglass, plastic, other polymers, crystals or polycrystalline silicateglass, and/or mixes of different types of materials, in any shape. Alsofor example, the particles 150 may be comprised of any of the variouspolymers described below, in a cured or solidified form.

In another representative or exemplary embodiment, diatoms, diatomaceousfrustules, and/or diatomaceous fragments or remains are utilized to formparticles 150, e.g., the cell walls (frustules) and frustule fragmentsof diatoms are utilized to form particles 150 and, accordingly, anyreference to a diatom should be understood to mean and include thefrustule or cell wall of a diatom, which is generally comprised of aform of silica, and/or any other diatomaceous fragments or remains, ofany shape or morphology. Diatoms are a major group of algae, are one ofthe most common types of phytoplankton, and may be considered a class(usually called Diatomophyceae) or a division or phylum (usually calledBacillariophyta, Bacillariophyceae, and/or Heterokontophyta), and allsuch orders, classes, divisions or phyla are considered within the scopeof the disclosure. Most diatoms are unicellular, although they can existas colonies in the shape of filaments or ribbons (e.g. Fragilaria), fans(e.g. Meridion), zigzags (e.g. Tabellaria), or stellate colonies (e.g.Asterionella). A typical feature of diatom cells is that they areencased within a cell wall made of silica (hydrated silicon dioxide)called a frustule. These frustules show a wide diversity in form, butusually consist of two asymmetrical sides with a split between them,hence the group name. Any and all types (over about 200 genera and100,000 species) of diatoms may be utilized as particles 150 including,for example and without limitation, centric diatoms (Centrales), pennatediatoms (Pennales) (with or without a raphe), and any and all diatoms,frustules, and/or diatomaceous fragments or remains are within the scopeof the disclosure and are individually and collectively referred toherein as “diatoms”.

It should also be noted that such diatoms may be available in a widevariety of sizes, including sizes greater than about 30 microns, and allsuch sizes of diatoms are within the scope of the disclosure. Forexample, in another representative embodiment, the plurality ofparticles are selected from the group consisting of: diatoms,diatomaceous frustules, diatomaceous fragments, diatomaceous remains,and mixtures thereof. For such an exemplary embodiment, the plurality ofparticles have a size (in any dimension) between about 0.5 to about 200microns, or more particularly between about 2.0 to about 100 microns, ormore particularly between about 2.0 to about 50 microns, or moreparticularly between about 4.0 to about 30 microns, or more particularlybetween about 5.0 to about 30 microns. For example and withoutlimitation, a representative diatom, diatomaceous frustule, diatomaceousfragment or other diatomaceous remains may have a size on the order ofabout 5 microns in diameter and about 20-30 microns in length.

Also in a representative embodiment, for any selected size of a particle150, there may be a comparatively narrow distribution or variance ofdiameter sizes, such as for a substantially spherical particle, tofacilitate comparatively dense packing of the particles 150 in a liquidor gel separator 200. For example and without limitation, for a 10micron selected particle size, it may be advantageous for the particlesto be within a 2 micron variance, e.g., 10 μ±2 μ, and multiplecomparatively narrow ranges are also within the scope of the disclosure,such as 7 μ±2 μ, 10 μ±1.5 μ, 15 μ±3 μ, 12 μ±1.5 μ, and so on.

In another representative embodiment, the particles are packed in one ormore layers, generally to be touching or abutting any adjacent particlesand, when not abutting, to be within a distance of about a one particlediameter (for the selected size of the particles 150) from its neighborsor more specifically, from adjacent particles. In an exemplaryembodiment, the plurality of particles 150 are substantially sphericaland densely packed in a monolayer, or a bilayer, or something inbetween, to provide a liquid or gel separator 200 having a thickness of1-2 particle diameters for the selected size of the particles 150, e.g.,a thickness of 1.5 particle diameters. In other exemplary embodiments,additional particle layers may also be utilized, such as an exemplaryliquid or gel separator 200 comprised of 3-6 layers of particles 150,also for example and without limitation.

The particles 150 and arrangement of particles 150 illustrated in FIG. 2reflect these additional considerations, and are illustrated assubstantially spherical particles, with very little variance ofdiameters, are comparatively densely packed to be either abutting orwithin one particle diameter of each other, and packed or arranged in amonolayer, i.e., the liquid or gel separator 200 has a thickness ofabout one particle 150 diameter and any additional liquid or gelpolymeric mixture 175.

In contrast, the particles 150 and arrangement of particles 150illustrated in FIG. 3 reflect considerably more variation, in size,shape, diameters, packing density, and arrangement into layers (shown astwo and three layers within the same liquid or gel separator 200). Forexample, such variations may be found or expected when naturallyoccurring particles 150 are utilized, such as diatoms, diatomaceousfrustules, diatomaceous fragments, diatomaceous remains, and mixturesthereof.

In addition, not separately illustrated in FIGS. 2 and 3, multipleprinted layers a liquid or gel separator printable composition may beutilized to form a liquid or gel separator 200.

It should be noted that the micro (sub-millimeter) size of the particles150, namely, microparticle sizes ranging substantially from about 0.5 to50 microns (or diatoms, diatomaceous frustules, diatomaceous fragments,diatomaceous remains, and mixtures thereof generally ranging from about5 to about 200 microns), along with the dense and abutting packing ofthe particles in the liquid or gel separator 200, is a substantialdeparture from prior art membrane separators, such as those usingsignificantly larger and regularly spaced-apart particles.

Representative diatoms, diatomaceous frustules, diatomaceous fragments,and diatomaceous remains have been obtained and are generally availablefrom Continental Chemical USA of Fort Lauderdale, Fla., US, and fromLintech International LLC of Macon, Ga., US. Representativesubstantially spherical particles comprised of silicate glass have beenobtained and are generally available from Potter Industries ofBrownwood, Tex., US.

It should also be noted that using diatoms (including diatomaceousfrustules, diatomaceous fragments, diatomaceous remains, and mixturesthereof) to form particles 150 provides serendipitous and unexpectedresults, as such diatoms (including diatomaceous frustules, diatomaceousfragments, diatomaceous remains, and mixtures thereof) are not generallyused in electronic devices such as batteries and supercapacitors. Thediatoms, diatomaceous frustules, diatomaceous fragments, anddiatomaceous remains are comparatively very hard and structurally sound,and can withstand the compressive and other forces exerted in adeposition process such as printing. The diatoms, diatomaceousfrustules, diatomaceous fragments, and diatomaceous remains areelectrically nonconductive, comparatively inexpensive, and highly porous(nanoporous), allowing and facilitating the movement or flow of one ormore ionic liquid and other electrolytes during charging and dischargingcycles.

The particles 150 prevent electrical contact between first conductor110, 110A and second conductor 115, and generally further preventelectrical contact between layers 120 and 125 (which, for example, mayfunction as anode and cathode of a battery). The rigidity of particles150 makes it possible to print a next layer on a printed liquid or gelseparator 200 by pressure applied techniques (like screen printing)without creating an electrical short in the representative energystorage device 100, 101. As previously mentioned, the representativeenergy storage device 100, 101 may be printed in line, adding layerssuccessively, without folding or lamination, for example. The polymergel with one or more embedded ionic liquids and/or other electrolyteprovides ionic conductivity. The ionic conductance will be realizedthrough the liquid or gel polymeric mixture 175 as well as on theexterior and/or interior (such as for diatoms) surfaces of particles150.

Ionic liquids are molten salts that at room temperature haveimmeasurably low vapor pressure, are non-flammable, have high ionicconductivity, have a wide range of thermal and electrochemicalstabilities. More generally, an ionic liquid is any of one or moreorganic molten salts which substantially consist only of ions and areliquid at temperatures below about 100° C. An ionic liquid is highlysuitable for deposition through printing, as they are non-volatile atroom temperatures. An ionic liquid may be selected based upon stabilityover time and temperature, a comparatively wide electrochemical windowor decomposition voltage, comparatively high conductivity, capability todisperse CNTs, a lack of corrosiveness (for other components, such asconductors), purity, and aprotic characteristics (to avoid hydrogen iondischarge at the cathodes). Representative ionic liquids utilized hereinform ion conducting gels with polymers when mixing or afterpolymerization of monomers in an ionic liquid media.

Ionic liquid cations are mostly organic and can be classified asammonium-based, imidazolium-based, piperidinium-based, pyridinium-based,pyrrolidinium-based, phosphonium-based, sulphonium-based, etc. based.Ionic liquid anions can be inorganic like tetrafluoroborate-based,hexafluorophosphate-based, chloride-based, nitrate-based,sulphate-based, etc. and organic like acetate-based,(triflluoromethylsulfonyl)imide-based, triflate-based, etc. Any and allionic liquids are within the scope of the disclosure.

The ionic liquid electrolyte, in a representative embodiment, comprisesa combination of one or more types of ionic liquid cations and/or one ormore types of ionic liquid anions, and there may be a wide variety ofany such combinations of ionic liquid anions and/or cations. Inaddition, any selected ionic liquid cation or ionic liquid anion may bepaired with any other type of ion (anion or cation respectively) whichis not an ionic liquid electrolyte, including any another type of anionor cation, such as a salt dissolved in water or another solvent or asalt of an ionic liquid, e.g., lithiumbis(trifluoromethylsulfonyl)imide, also for example and withoutlimitation. For example and without limitation, a selected ionic liquidelectrolyte combination may include an ionic liquid cation, an ionicliquid anion, a selected salt and a solvent. Also for example andwithout limitation, a selected ionic liquid electrolyte combination mayinclude an ionic liquid cation or anion and an anion or cation which isnot an ionic liquid, such as lithium bis(trifluoromethylsulfonyl)imidementioned above.

In a representative embodiment, for example and without limitation, arepresentative ionic liquid cation may be selected from the groupconsisting of: butyltrimethylammonium, 1-ethyl-3-methylimidazolium,1-butyl-3-methylimidazolium, 1-methyl-3-propylimidazolium,1-hexyl-3-methylimidazolium, choline, ethylammonium,tributylmethylphosphonium, tributyl(tetradecyl)phosphonium,trihexyl(tetradecyl)phosphonium, 1-ethyl-2,3-methylimidazolium,1-butyl-1-methylpiperidinium, diethylmethylsulfonium ,1-methyl-3-propylimidazolium, 1-methyl-1-propylpiperidinium,1-butyl-2-methylpyridinium, 1-butyl-4-methylpyridinium,1-butyl-1-methylpyrrolidinium, and mixtures thereof.

Also for example and without limitation, a representative ionic liquidanion or other type of anion may be selected from the group consistingof: tris(pentafluoroethyl)trifluorophosphate, trifluoromethanesulfonate,hexafluorophosphate, tetrafluoroborate, ethyl sulfate, methyl sulfate,dimethyl phosphate, trifluoromethanesulfonate, methanesulfonate,triflate, tricyanomethanide, dibutylphosphate,bis(trifluoromethylsulfonyl)imide, bis-2,4,4-(trimethylpentyl)phosphinate, iodide, chloride, bromide, nitrate, thiocyanate, andmixtures thereof.

Continuing with the examples, a representative combination of ionicliquid electrolytes (anions and cations) and other electrolytecompositions, in a representative embodiment, comprises one or moreionic liquid electrolyte anions, cations and/or other compounds, salts,mixtures, or other anions or cations, for example and withoutlimitation, and may be selected from the group consisting of:butyltrimethylammonium bis(trifluoromethylsulfonyl)imide,1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide,1-methyl-3-propylimidazolium bis(trifluoromethylsulfonyl)imide,1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, cholinebis(trifluoromethylsulfonyl)imide, ethylammonium nitrate,tributylmethylphosphonium methylsulfate, 1-ethyl-2,3-methylimidazoliumtetrafluoroborate, 1-butyl-1-methylpiperidinium iodide,diethylmethylsulfonium bis(trifluoromethylsulfonyl)imide,1-methyl-3-propylimidazolium iodide, 1-ethyl-3-methylimidazoliumthiocyanate, 1-methyl-1-propylpiperidiniumbis(trifluoromethylsulfonyl)imide, 1-butyl-2-methylpyridiniumbis(trifluoromethylsulfonyl)imide, 1-butyl-4-methylpyridiniumbis(trifluoromethylsulfonyl)imide, 1-butyl-1-methylpyrrolidiniumbis(trifluoromethylsulfonyl)imide, diethylmethylsulfoniumbis(trifluoromethylsulfonyl)imide, including salts, such as metallicsalts such as lithium, zinc, silver, cadmium and nickel of thefollowing: bis(trifluoromethylsulfonyl)imide,tris(pentafluoroethyl)trifluorophosphate, trifluoromethanesulfonate,hexafluorophosphate, tetrafluoroborate, ethyl sulfate, dimethylphosphate, trifluoromethanesulfonate, triflate, tricyanomethanide,dibutylphosphate, and mixtures thereof. Other ionic liquids as utilizedin the electronic and electrochemical arts may also be suitable, and areconsidered equivalent and within the scope of the disclosure.

Ionic liquids used in supercapacitors, for example and withoutlimitation, may be 1-ethyl-3-methylimidazoliumbis(trifluoromethylsulfonyl)imide, and/or 1-ethyl-3-methylimidazoliumethyl sulfate. Ionic liquids used for batteries, also for example andwithout limitation, may be 1-ethyl-3-methylimidazoliumtetrafluoroborate, tributyl(tetradecyl)phosphonium methansulfonate,and/or trihexyl (tetradecyl) phosphoniumbis(trifluoromethylsulfonyl)imide. Also for example and withoutlimitation, 1-ethyl-3-methylimidazolium tetrafluoroborate may be used ina zinc-carbon battery and tributyl(tetradecyl)phosphoniummethansulfonate, trihexyl (tetradecyl) phosphoniumbis(trifluoromethylsulfonyl)imide may be used for zinc-silver oxidebatteries. Representative ionic liquids may be obtained from IoLiTecIonic Liquids Technologies GmbH of Heilbronn, Germany and CytecIndustries Inc. of Woodland Park, N.J. USA.

A representative liquid or gel separator printable composition (or ink)and a resulting representative liquid or gel separator 200 may furthercomprise one or more additional, second electrolyte different from thefirst electrolyte, such as an acid, a base, a salt dissolved in asolvent (e.g., water, an organic solvent), or a salt dissolvable ormiscible in an ionic liquid, to form free ions. In a representativeembodiment, a second electrolyte comprises one or more electrolytesselected from the group consisting of: potassium hydroxide, sodiumhydroxide, ammonium hydroxide, lithium hydroxide, nickel hydroxide,cadmium hydroxide, magnesium hydroxide, sulfuric acid, hydrochloricacid, fluoroboric acid, ammonium chloride, zinc chloride, zincbis(trifluoromethanesulfonyl)imide, aluminium chloride, chromiumchloride, magnesium perchloride, barium chromate, lithium chromate,lithium-thyonyl chloride, lithiujm perchlorate, lithium bromide, lithiumtriflate, lithium hexafluorophosphate, lithium tetrafluoroborate,lithium bis-oxalato borate, lithium bis(trifluoromethanesulfonyl)imide,lithium bisoxalatoborate, lithium iodide, lithium tetrachloroaluminate,potassium carbonate, potassium fluoride, potassium borate, silvernitride, silver tetrafluoroborate; and mixtures thereof.

Also forming the liquid or gel separator printable composition andresulting liquid or gel separator 200 are one or more polymers (orequivalently, polymeric precursors or polymerizable precurors in theprintable composition which are in turn in a polymerized, cured or driedform in the liquid or gel separator 200), or viscosity modifiers,binders, resins or thickeners (as a viscosity modifier) (orequivalently, a viscous compound, a viscous resin, a viscous agent, aviscous polymer, a viscous resin, a viscous binder, a thickener, and/ora rheology modifier) may be used, for example and without limitation:polymers (or equivalently, polymeric precursors or polymerizableprecurors) such as polyvinyl pyrrolidone (“PVP”, also referred to orknown as polyvinyl pyrrolidinone), polyvinyl alcohol (“PVA”),polyvinylidene fluoride (“PVFD”), polyvynylidenefluoride-trifluoroethylene, polytetrafluoroethylene (“PTFE”),polydimethylsiloxane, polyethelene, polypropylene, polyethylene oxide,polypropylene oxide, polyethylene glycolhexafluoropropylene,polyethylene terefphtalatpolyacrylonitryle, polyvinylalcogel,polyvinylpyrrolidone, polyvynilchloride, polyvinyl butyral; polyimidepolymers and copolymers (including aliphatic, aromatic and semi-aromaticpolyimides) such as polyamide, polyaramides, polyacrylamide; acrylateand (meth)acrylate polymers and copolymers such aspolymethylmethacrylate, polyacrylonitrile, acrylonitrile butadienestyrene, allylmethacrylate, polyvinylcaprolactam, polystyrene,polybutadiene, polybutylene terephthalate, polycarbonate,polychloroprene, polyethersulfone, nylon, styrene-acrylonitrile resin;clays such as hectorite clays, garamite clays, organo-modified clays;saccharides and polysaccharides such as guar gum, xanthan gum, starch,butyl rubber, agarose, pectin; celluloses and modified celluloses suchas hydroxy methylcellulose, methylcellulose, ethyl cellulose, propylmethylcellulose, methoxy cellulose, methoxy methylcellulose, methoxypropyl methylcellulose, hydroxy propyl methylcellulose, carboxymethylcellulose, hydroxy ethylcellulose, ethyl hydroxyl ethylcellulose,cellulose ether, cellulose ethyl ether, chitosan; fumed silica (such asCabosil), silica powders and modified ureas such as BYK® 420 (availablefrom BYK Chemie GmbH); and mixtures thereof. As mentioned above, some ofthe viscosity modifiers may also function as solvents and vice-versa,such as the various glycols, and therefore are included in the variouslistings of representative solvents and viscosity modifiers. In anexemplary embodiment, the PVA utilized has a molecular weight betweenabout 10,000 to about 250,000 MW, while the PVDF has a molecular weightbetween about 1,000 to about 500,000 MW, and may be obtainedrespectively from Polysciences, Inc. of Warrington, Pa. USA and Arkemaof King of Prussia, Pa. USA. PTFE may be obtained from DuPont, ofWilmington, Del., USA. In various embodiments, E-3 and E-10 celluloseresins available from The Dow Chemical Company (www.dow.com) andHercules Chemical Company, Inc. (www.herchem.com) may be utilized. Otherviscosity modifiers may be used, as well as particle addition to controlviscosity, as described in Lewis et al., Patent Application PublicationPub. No. U.S. 2003/0091647. Other viscosity modifiers or binders mayalso be utilized. Any of these various polymers may also be utilized toform a sealant 35. The resulting composition may have a viscositysubstantially about 50 cps to about 25,000 cps at about 25° C., and maybe adjusted depending upon the deposition technique to be utilized, forexample: for screen printing, the composition may have a viscositybetween about 1,000 centipoise (cps) and 25,000 cps at 25° C., or morespecifically between about 6,000 cps and 15,000 cps at 25° C., or morespecifically between about 8,000 cps and 12,000 cps at 25° C., or morespecifically between about 9,000 cps and 11,000 cps at room temperature;while for flexographic printing, the composition may have a viscositybetween about 1,000 cps and 10,000 cps at 25° C., or more specificallybetween about 1,500 cps and 4,000 cps at 25° C., or more specificallybetween about 1,700 cps and 3,000 cps at 25° C., or more specificallybetween about 1,800 cps and 2,200 cps at room temperature.

Various solvents may also be utilized to form liquid or gel separatorprintable composition (and trace amount or more may remain in theresulting liquid or gel separator 200), such as, for example, to adjustviscosity or other properties of the liquid or gel separator printablecomposition. One or more solvents (as first, second, third fourth, etc.,solvents) may be used equivalently, for example and without limitation:solvents selected from the group consisting of: water; alcohols such asmethanol, ethanol, N-propanol (including 1-propanol, 2-propanol(isopropanol or IPA), 1-methoxy-2-propanol), butanol (including1-butanol, 2-butanol (isobutanol)), pentanol (including 1-pentanol,2-pentanol, 3-pentanol), hexanol (including 1-hexanol, 2-hexanol,3-hexanol), octanol, N-octanol (including 1-octanol, 2-octanol,3-octanol), tetrahydrofurfuryl alcohol (THFA), cyclohexanol,cyclopentanol, terpineol; lactones such as butyl lactone; ethers such asmethyl ethyl ether, diethyl ether, ethyl propyl ether, and polyethers;ketones, including diketones and cyclic ketones, such as cyclohexanone,cyclopentanone, cycloheptanone, cyclooctanone, acetone, benzophenone,acetylacetone, acetophenone, cyclopropanone, isophorone, methyl ethylketone; esters such ethyl acetate, dimethyl adipate, proplyene glycolmonomethyl ether acetate, dimethyl glutarate, dimethyl succinate,glycerin acetate, carboxylates; glycols such as ethylene glycols,diethylene glycols, polyethylene glycols, propylene glycols, dipropyleneglycols, glycol ethers, glycol ether acetates; carbonates such aspropylene carbonate; glycerols and other polyols and polymeric polyolsor glycols such as glycerin, diol, triol, tetraol, pentaol, ethyleneglycol, 1,4-butanediol, 1,2-butanediol, 2,3-butanediol, 1,3-propanediol,1,4-butanediol, 1,5-pentanediol, 1,8-octanediol, 1,2-propanediol,1,3-butanediol, 1,2-pentanediol, etohexadiol, p-menthane-3,8-diol,2-methyl-2,4-pentanediol; tetramethyl urea, n-methylpyrrolidone,acetonitrile, tetrahydrofuran (THF), dimethyl formamide (DMF), N-methylformamide (NMF), dimethyl sulfoxide (DMSO), thionyl chloride; sulfurylchloride; and mixtures thereof. Any of these various solvents may alsofurther comprise an acid or a base (liquid or dissolved solid), such asto adjust overall pH (or pK), including inorganic and/or organic acidssuch as carboxylic acids (including dicarboxylic acids, tricarboxylicacids, alkyl carboxylic acids, and so on, e.g., dicarboxylic acids suchas propanedioic (malonic) acid, butanedioic (succinic) acid,pentanedioic (glutaric) acid, hexanedioic (adipic) acid, heptanedioic(pimelic) acid, octanedioic (suberic) acid, nonanedioic (azelaic) acid,decanedioic (sebacic) acid, undecanedioic acid, dodecanedioic acid,tridecanedioic (brassylic) acid, tetradecanedioic acid, pentadecanedioicacid, hexadecanedioic (thapsic) acid, octadecanedioic acid); aceticacid; oxalic acid; mellitic acid; formic acid, chloroacetic acid;benzoic acid; trifluoroacetic acid; propanoic acid; butanoic acid;hydrochloric acid; sulfuric acid; carbonic acid; and bases such asammonium hydroxide, sodium hydroxide, potassium hydroxide; and mixturesthereof.

A conductive substrate utilized to form a first conductor or conductivelayer 110A may be any type of prefabricated substrate 105 discussedbelow which has been coated or otherwise has deposited a conductor orconductive layer (e.g., a first conductor 110 as described above andbelow). A conductive substrate utilized to form a first conductor orconductive layer 110A may be any type of conductor, mixture ofconductors, alloys of conductors, etc., including those discussed aboveand below, which has or have a form factor suitable for deposition ofthe layer 120 or 125 such as, for example and without limitation, aconductive foil or sheet, such as an aluminum foil, a nickel foil, acarbon foil, a carbon foam sheet, a CNT foil, a graphene foil, a silverfoil, a gold foil, an iron sheet, a steel sheet, other types of sheetmetal, etc.

The substrate (or base) 105 may be comprised of any suitable material,such as plastic, paper, cardboard, or coated paper or cardboard, forexample and without limitation. The substrate 105 may comprise anyflexible or nonflexible material having the strength and degree ofelectrical insulation to withstand the intended use conditions. In anexemplary embodiment, a substrate 105 comprises a polyester or plasticsheet, such as a CT-7 seven mil polyester sheet treated for printreceptiveness commercially available from MacDermid Autotype, Inc. ofMacDermid, Inc. of Denver, Colo., USA, for example. In another exemplaryembodiment, a substrate 105 comprises a polyimide film such as Kaptoncommercially available from DuPont, Inc. of Wilmington Del., USA, alsofor example. Also in an exemplary embodiment, substrate 105 comprises amaterial having a dielectric constant capable of or suitable forproviding sufficient electrical insulation for the excitation anddischarge voltages which may be selected. A substrate 105 may comprise,also for example, any one or more of the following: paper, coated paper,plastic coated paper, fiber paper, cardboard, poster paper, posterboard, books, magazines, newspapers, wooden boards, plywood, and otherpaper or wood-based products in any selected form; plastic or polymermaterials in any selected form (sheets, film, boards, and so on);natural and synthetic rubber materials and products in any selectedform; natural and synthetic fabrics in any selected form; glass,ceramic, and other silicon or silica-derived materials and products, inany selected form; building materials and products; or any otherproduct, currently existing or created in the future. In a firstexemplary embodiment, a substrate 105 may be selected which provides adegree of electrical insulation (i.e., has a dielectric constant orinsulating properties sufficient to provide electrical insulation of theone or more first conductors 110 deposited or applied on a first (front)side of the substrate 105), either electrical insulation from each otheror from other apparatus or system components. For example, whilecomparatively expensive choices, a glass sheet or a silicon wafer alsocould be utilized as a substrate 105. In other exemplary embodiments,however, a plastic sheet or a plastic-coated paper product is utilizedto form the substrate 105 such as the polyester mentioned above orpatent stock and 100 lb. cover stock available from Sappi, Ltd., orsimilar coated papers from other paper manufacturers such as MitsubishiPaper Mills, Mead, and other paper products. In another exemplaryembodiment, an embossed plastic sheet or a plastic-coated paper producthaving a plurality of grooves, also available from Sappi, Ltd. isutilized, with the grooves utilized for forming the conductors 110.Suitable substrates 105 also potentially include extruded polyolefinicfilms, including LDPE films; polymeric nonwovens, including carded,meltblown and spunbond nowovens, and cellulosic paper. The substrate 105may also comprise laminates of any of the foregoing materials. Two ormore laminae may be adhesively joined, thermally bonded, or autogenouslybonded together to form the laminate comprising the substrate. Ifdesired, the laminae may be embossed.

The exemplary substrate 105 (or conductive substrate utilized to form afirst conductor or conductive layer 110A) as illustrated in the variousFigures has a form factor which is substantially flat in an overallsense, such as comprising a sheet of a selected material (e.g., paper orplastic or foil) which may be fed through a printing press, for exampleand without limitation, and which may have a topology on a first surface(or side) which includes surface roughness, cavities, channels orgrooves or having a first surface which is substantially smooth within apredetermined tolerance (and does not include cavities, channels orgrooves). Those having skill in the art will recognize that innumerable,additional shapes and surface topologies are available, are consideredequivalent and within the scope of the disclosure.

The first and second conductors (which also may be considered electrodesor current collectors) 110 (110A), 115 may be comprised of any suitablematerial, applied or deposited (on a first side or surface of thesubstrate 105), such as through a printing process, to a thicknessdepending upon the type of conductive ink or polymer and the selectedembodiment, such as to about 0.1 to 6 microns (e.g., about 3 microns fora typical silver ink, gold ink, aluminum ink, and to less than onemicron for a nanosilver ink), for example and without limitation. In anexemplary method of manufacturing the representative energy storagedevice 100, 101 embodiments, a conductive ink, polymer, or otherconductive liquid or gel (such as a silver (Ag) ink or polymer, a nanosilver ink composition, a carbon nanotube ink or polymer, orsilver/carbon mixture such as amorphous nanocarbon (having particlesizes between about 75-100 nm) dispersed in a silver ink) is depositedon a substrate 105, such as through a printing or other depositionprocess, and may be subsequently cured or partially cured (such asthrough an ultraviolet (uv) curing process), to form the one or morefirst conductors 110. Similar processes may also be utilized to form asecond conductor 115. In another exemplary embodiment, the one or morefirst and second conductors 110, 115 may be formed by sputtering, spincasting (or spin coating), vapor deposition, or electroplating of aconductive compound or element, such as a metal (e.g., aluminum, copper,silver, gold, nickel, palladium). Combinations of different types ofconductors and/or conductive compounds or materials (e.g., ink, polymer,elemental metal, etc.) may also be utilized to generate one or morecomposite first and second conductors 110, 115. Multiple layers and/ortypes of metal or other conductive materials may be combined to form theone or more first and second conductors 110 (110A), 115. In variousexemplary embodiments, a plurality of first and second conductors 110(110A), 115 are deposited, and in other embodiments, a first or secondconductor 110 (110A), 115 may be deposited as a single conductive sheetor otherwise attached (e.g., a sheet of aluminum coupled to a substrate105) (not separately illustrated).

Other conductive inks or materials may also be utilized to form the oneor more first and second conductors 110, 115, such as copper, tin,aluminum, gold, noble metals, carbon, carbon foam, carbon black, singleor double or multi-walled CNTs, graphene, graphene platelets,nanographene platelets, nanocarbon and nanocarbon and silvercompositions, nano silver compositions (including nanosilver fiber andnanosilver particle inks), or other organic or inorganic conductivepolymers, inks, gels or other liquid or semi-solid materials. Arepresentative conductive ink is disclosed in U.S. patent applicationSer. No. 13/360,999, filed Jan. 30, 2012, entitled “Metallic NanofiberInk, Substantially Transparent Conductor, and Fabrication Method” (the“second related patent application”), the entire contents of which areincorporated herein by reference with the same full force and effect asif set forth in their entirety herein, and with priority claimed for allcommonly disclosed subject matter. In an exemplary embodiment, carbonblack (having a particle diameter of about 100 nm) is added to a silverink to have a resulting carbon concentration in the range of about0.025% to 0.1%. In addition, any other printable or coatable conductivesubstances may be utilized equivalently to form the first and secondconductors 110, 115, and exemplary conductive compounds include: (1)from Conductive Compounds (Londonberry, N.H., USA), AG-500, AG-800 andAG-510 Silver conductive inks, which may also include an additionalcoating UV-10065 ultraviolet curable dielectric (such as part of a firstdielectric layer 125); (2) from DuPont, 7102 Carbon Conductor (ifoverprinting 5000 Ag), 7105 Carbon Conductor, 5000 Silver Conductor,7144 Carbon Conductor (with UV Encapsulants), 7152 Carbon Conductor(with 7165 Encapsulant), and 9145 Silver Conductor; (3) from SunPoly,Inc., 128A Silver conductive ink, 129A Silver and Carbon Conductive Ink,140A Conductive Ink, and 150A Silver Conductive Ink; (4) from DowCorning, Inc., PI-2000 Series Highly Conductive Silver Ink; (5) fromHenkel/Emerson & Cumings, Electrodag 725A; and (6) Monarch M120available from Cabot Corporation of Boston, Mass., USA, for use as acarbon black additive, such as to a silver ink to form a mixture ofcarbon and silver ink. In addition, conductive inks and compounds may beavailable from a wide variety of other sources.

Conductive polymers which also may be substantially opticallytransmissive may also be utilized to form the one or more first andsecond conductors 110, 115. For example, polyethylene-dioxithiophene maybe utilized, such as the polyethylene-dioxithiophene commerciallyavailable under the trade name “Orgacon” from AGFA Corp. of RidgefieldPark, N.J., USA, in addition to any of the other transmissive conductorsdiscussed below and their equivalents. Other conductive orsemiconductive polymers, without limitation, which may be utilizedequivalently include polyaniline and polypyrrole polymers, for example.In another exemplary embodiment, carbon nanotubes which have beensuspended or dispersed in a polymerizable ionic liquid or other fluidsare utilized to form various conductors which are substantiallyoptically transmissive or transparent.

Organic semiconductors, variously called π-conjugated polymers,conducting polymers, or synthetic metals, are inherently semiconductivedue to π-conjugation between carbon atoms along the polymer backbone,and also may be utilized to form first and second conductors 110 (110A),115. Their structure contains a one-dimensional organic backbone whichenables electrical conduction following n− or p+ type doping.Well-studied classes of organic conductive polymers includepoly(acetylene)s, poly(pyrrole)s, poly(thiophene)s, polyanilines,polythiophenes, poly(p-phenylene sulfide), poly(para-phenylenevinylene)s (PPV) and PPV derivatives, poly(3-alkylthiophenes),polyindole, polypyrene, polycarbazole, polyazulene, polyazepine,poly(fluorene)s, and polynaphthalene. Other examples includepolyaniline, polyaniline derivatives, polythiophene, polythiophenederivatives, polypyrrole, polypyrrole derivatives, polythianaphthene,polythianaphthane derivatives, polyparaphenylene, polyparaphenylenederivatives, polyacetylene, polyacetylene derivatives, polydiacethylene,polydiacetylene derivatives, polyparaphenylenevinylene,polyparaphenylenevinylene derivatives, polynaphthalene, andpolynaphthalene derivatives, polyisothianaphthene (PITN),polyheteroarylenvinylene (ParV), in which the heteroarylene group canbe, e.g., thiophene, furan or pyrrol, polyphenylene-sulphide (PPS),polyperinaphthalene (PPN), polyphthalocyanine (PPhc) etc., and theirderivatives, copolymers thereof and mixtures thereof. As used herein,the term derivatives means the polymer is made from monomers substitutedwith side chains or groups.

The method for polymerizing the conductive polymers is not particularlylimited, and the usable methods include uv or other electromagneticpolymerization, heat polymerization, electrolytic oxidationpolymerization, chemical oxidation polymerization, and catalyticpolymerization, for example and without limitation. The polymer obtainedby the polymerizing method is often neutral and not conductive untildoped. Therefore, the polymer is subjected to p-doping or n-doping to betransformed into a conductive polymer. The semiconductor polymer may bedoped chemically, or electrochemically. The substance used for thedoping is not particularly limited; generally, a substance capable ofaccepting an electron pair, such as a Lewis acid, is used. Examplesinclude hydrochloric acid, sulfuric acid, organic sulfonic acidderivatives such as parasulfonic acid, polystyrenesulfonic acid,alkylbenzenesulfonic acid, camphorsulfonic acid, alkylsulfonic acid,sulfosalycilic acid, etc., ferric chloride, copper chloride, and ironsulfate.

In a representative or exemplary embodiment for a battery, a layer 120such as an anode is formed by printing (on a first conductor (electrodeor current collector) 110, 110A such as aluminum foil) using an anodeink comprising about 85% zinc (in powder or particle form), about0.5-1.0% PVDF, and about 14% tetramethylurea orN-methyl-2-pyrrolidinone, and after curing and/or drying, the anodelayer 120 generally comprises zinc and PVDF, and any trace amounts ofthe solvents, and is about 5-60 microns thick.

In a representative or exemplary embodiment for a battery, a layer 125such as a cathode is formed by printing (over the liquid or gelseparator 200) using a cathode ink comprising about 41% manganesedioxide (in powder or particle form), about 3.5% conductive graphitepowder, about 1.0-2.5% PVDF, and about 53% tetramethylurea orN-methyl-2-pyrrolidinone, and after curing and/or drying, the cathodelayer 125 generally comprises manganese dioxide, graphite and PVDF, andany trace amounts of the solvents, and is about 5-60 microns thick.

Also in a representative or exemplary embodiment for a battery, a liquidor gel separator printable composition comprises about 52.7% silicateglass spheres having a diameter of about 7 microns each, about 2.8% PVDFor PVA, about 19.6% N-methyl-2-pyrrolidinone, and about 24.9% of anelectrolyte comprising zinc tetrafluoroborate salt dissolved in1-ethyl-3-methylimidalzolium tetrafluoroborate ionic liquid, with theresulting liquid or gel separator 200 generally having a thickness ofabout double the diameters of the particles 150, such as about 10-15microns, and comprising the glass spheres, the PVDF or PVA, and theelectrolytes.

Those having skill in the electronic or printing arts will recognizeinnumerable variations in the ways in which the one or more first andsecond conductors 110, 110A, 115, layers 120 and 125 (anode and cathodelayers), and liquid or gel separator 200, may be formed, with all suchvariations considered equivalent and within the scope of the disclosure.For example, any of the one or more first and second conductors 110,110A, 115, layers 120 and 125 (anode and cathode layers), and liquid orgel separator 200 may also be deposited through sputtering or vapordeposition, without limitation. In addition, for other variousembodiments, the one or more first and second conductors 110, 115 may bedeposited as a single or continuous layer, such as through coating,printing, sputtering, or vapor deposition, such as to form multipleelectrodes or battery cells. Those having skill in the electronic orprinting arts also will recognize innumerable variations in the ways inwhich the liquid or gel separator 200 and any of the layers 120 and 125(anode and cathode layers) may be deposited, such as through printing,with all such variations considered equivalent and within the scope ofthe disclosure.

As a consequence, as used herein, “deposition” includes any and allprinting, coating, rolling, spraying, layering, sputtering, plating,spin casting (or spin coating), vapor deposition, lamination, affixingand/or other deposition processes, whether impact or non-impact, knownin the art. “Printing” includes any and all printing, coating, rolling,spraying, layering, spin coating, lamination and/or affixing processes,whether impact or non-impact, known in the art, and specificallyincludes, for example and without limitation, screen printing, inkjetprinting, electro-optical printing, electroink printing, photoresist andother resist printing, thermal printing, laser jet printing, magneticprinting, pad printing, flexographic printing, hybrid offsetlithography, Gravure and other intaglio printing, for example. All suchprocesses are considered deposition processes herein and may beutilized. The exemplary deposition or printing processes do not requiresignificant manufacturing controls or restrictions. No specifictemperatures or pressures are required. Some clean room or filtered airmay be useful, but potentially at a level consistent with the standardsof known printing or other deposition processes. For consistency,however, such as for proper alignment (registration) of the varioussuccessively deposited layers forming the various embodiments,relatively constant temperature (with possible exceptions, discussedbelow, such as for applied heat for bonding) and humidity may bedesirable. In addition, the various compounds utilized may be containedwithin various polymers, binders or other dispersion agents which may beheat-cured or dried, air dried under ambient conditions, or IR or uvcured.

It should also be noted, generally for any of the applications ofvarious compounds herein, such as through printing or other deposition,the surface properties or surface energies may also be controlled, suchas through the use of resist coatings or by otherwise modifying the“wetability” of such a surface, for example, by modifying thehydrophilic, hydrophobic, or electrical (positive or negative charge)characteristics, for example, of surfaces such as the surface of thesubstrate 105, the surfaces of the various first and second conductors110, 115, and/or other surfaces formed during fabrication. Inconjunction with the characteristics of the compound, suspension,polymer or ink being deposited, such as the surface tension, thedeposited compounds may be made to adhere to desired or selectedlocations, and effectively repelled from other areas or regions.

Representative embodiments provide a liquid or gel separator utilized toseparate and space apart first and second electrodes of an energystorage device, such as a battery or a supercapacitor, which is formedfrom a composition that is capable of being printed on a wide variety ofsurfaces, including irregular, uneven or otherwise non-smooth surfaces,for example and without limitation. A resulting representative liquid orgel separator also may be flexible and capable of being printed orotherwise applied in a wide variety of configurations, shapes, and formfactors. An exemplary liquid or gel separator also may be comparativelythin and minimizes or diminishes resistivity or other impedance, andfurther has a comparatively high ionic conductivity. In addition, arepresentative embodiment of a liquid or gel separator has sufficientstructural strength and integrity to allow and facilitate the printingof additional layers, such as additional electrodes and interveningenergy storage materials and compositions.

Although the invention has been described with respect to specificembodiments thereof, these embodiments are merely illustrative and notrestrictive of the invention. In the description herein, numerousspecific details are provided, such as examples of electroniccomponents, electronic and structural connections, materials, andstructural variations, to provide a thorough understanding ofembodiments of the present invention. One skilled in the relevant artwill recognize, however, that an embodiment of the invention can bepracticed without one or more of the specific details, or with otherapparatus, systems, assemblies, components, materials, parts, etc. Inother instances, well-known structures, materials, or operations are notspecifically shown or described in detail to avoid obscuring aspects ofembodiments of the present invention. One having skill in the art willfurther recognize that additional or equivalent method steps may beutilized, or may be combined with other steps, or may be performed indifferent orders, any and all of which are within the scope of theclaimed invention. In addition, the various Figures are not drawn toscale and should not be regarded as limiting.

Reference throughout this specification to “one embodiment”, “anembodiment”, or a specific “embodiment” means that a particular feature,structure, or characteristic described in connection with the embodimentis included in at least one embodiment and not necessarily in allembodiments, and further, are not necessarily referring to the sameembodiment. Furthermore, the particular features, structures, orcharacteristics of any specific embodiment may be combined in anysuitable manner and in any suitable combination with one or more otherembodiments, including the use of selected features withoutcorresponding use of other features. In addition, many modifications maybe made to adapt a particular application, situation or material to theessential scope and spirit of the present invention. It is to beunderstood that other variations and modifications of the embodiments ofthe present invention described and illustrated herein are possible inlight of the teachings herein and are to be considered part of thespirit and scope of the present invention.

It will also be appreciated that one or more of the elements depicted inthe Figures can also be implemented in a more separate or integratedmanner, or even removed or rendered inoperable in certain cases, as maybe useful in accordance with a particular application. Integrally formedcombinations of components are also within the scope of the invention,particularly for embodiments in which a separation or combination ofdiscrete components is unclear or indiscernible. In addition, use of theterm “coupled” herein, including in its various forms such as “coupling”or “couplable”, means and includes any direct or indirect electrical,structural or magnetic coupling, connection or attachment, or adaptationor capability for such a direct or indirect electrical, structural ormagnetic coupling, connection or attachment, including integrally formedcomponents and components which are coupled via or through anothercomponent.

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm.”

All documents cited in the Detailed Description are, in relevant part,incorporated herein by reference; the citation of any document is not tobe construed as an admission that it is prior art with respect to thepresent invention. To the extent that any meaning or definition of aterm in this document conflicts with any meaning or definition of thesame term in a document incorporated by reference, the meaning ordefinition assigned to that term in this document shall govern.

Furthermore, any signal arrows in the drawings/Figures should beconsidered only exemplary, and not limiting, unless otherwisespecifically noted. Combinations of components of steps will also beconsidered within the scope of the present invention, particularly wherethe ability to separate or combine is unclear or foreseeable. Thedisjunctive term “or”, as used herein and throughout the claims thatfollow, is generally intended to mean “and/or”, having both conjunctiveand disjunctive meanings (and is not confined to an “exclusive or”meaning), unless otherwise indicated. As used in the description hereinand throughout the claims that follow, “a”, “an”, and “the” includeplural references unless the context clearly dictates otherwise. Also asused in the description herein and throughout the claims that follow,the meaning of “in” includes “in” and “on” unless the context clearlydictates otherwise.

The foregoing description of illustrated embodiments of the presentinvention, including what is described in the summary or in theabstract, is not intended to be exhaustive or to limit the invention tothe precise forms disclosed herein. From the foregoing, it will beobserved that numerous variations, modifications and substitutions areintended and may be effected without departing from the spirit and scopeof the novel concept of the invention. It is to be understood that nolimitation with respect to the specific methods and apparatusillustrated herein is intended or should be inferred. It is, of course,intended to cover by the appended claims all such modifications as fallwithin the scope of the claims.

It is claimed:
 1. A composition for fabricating a liquid or gelseparator for separating and spacing apart at least two conductors, thecomposition comprising: a plurality of particles; an ionic liquid as afirst electrolyte, the ionic liquid comprising1-ethyl-3-methylimidazolium; a second electrolyte comprising zinctetrafluoroborate salt, the first and second electrolytes present in anamount between 15 to 30 percent of the total weight of the composition;and a polymer present in an amount between 0.5 to 10 percent of thetotal weight of the composition and comprising polyvinyl alcohol (“PVA”)or polyvinylidene fluoride (“PVFD”).
 2. The composition of claim 1,wherein the plurality of particles have a size between 5 microns to 15microns and are present in an amount between 40 to 60 percent of thetotal weight of the composition, and wherein the plurality of particlescomprise silicate glass or one or more diatomaceous particles ormixtures thereof.
 3. The composition of claim 2, wherein at least someparticles of the plurality of particles are hollow.
 4. The compositionof claim 1, further comprising: a solvent present in an amount between10 to 30 percent of the total weight of the composition, the solventcomprising one or more solvents selected from the group consisting of:water; alcohols such as methanol, ethanol, N-propanol (including1-propanol, 2-propanol (isopropanol or IPA), 1-methoxy-2-propanol),butanol (including 1-butanol, 2-butanol (isobutanol)), pentanol(including 1-pentanol, 2-pentanol, 3-pentanol), hexanol (including1-hexanol, 2-hexanol, 3-hexanol), octanol, N-octanol (including1-octanol, 2-octanol, 3-octanol), tetrahydrofurfuryl alcohol (THFA),cyclohexanol, cyclopentanol, terpineol; lactones such as butyl lactone;ethers such as methyl ethyl ether, diethyl ether, ethyl propyl ether,and polyethers; ketones, including diketones and cyclic ketones, such ascyclohexanone, cyclopentanone, cycloheptanone, cyclooctanone, acetone,benzophenone, acetylacetone, acetophenone, cyclopropanone, isophorone,methyl ethyl ketone; esters such ethyl acetate, dimethyl adipate,proplyene glycol monomethyl ether acetate, dimethyl glutarate, dimethylsuccinate, glycerin acetate, carboxylates; glycols such as ethyleneglycols, diethylene glycols, polyethylene glycols, propylene glycols,dipropylene glycols, glycol ethers, glycol ether acetates; carbonatessuch as propylene carbonate; glycerols and other polyols and polymericpolyols or glycols such as glycerin, diol, triol, tetraol, pentaol,ethylene glycol, 1,4-butanediol, 1,2-butanediol, 2,3-butanediol,1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,8-octanediol,1,2-propanediol, 1,3-butanediol, 1,2-pentanediol, etohexadiol,p-menthane-3,8-diol, 2-methyl-2,4-pentanediol; tetramethyl urea,n-methylpyrrolidone, N-methyl-2-pyrrolidinone,acetonitrile,tetrahydrofuran (THF), dimethyl formamide (DMF), N-methyl formamide(NMF), dimethyl sulfoxide (DMSO); thionyl chloride; sulfuryl chloride;and mixtures thereof.
 5. The composition of claim 1, wherein theplurality of particles are selected from the group consisting of:diatoms, diatomaceous frustules, diatomaceous fragments, diatomaceousremains, and mixtures thereof.
 6. The composition of claim 1, whereinthe first electrolyte further comprises one or more ionic liquid cationsselected from the group consisting of: butyltrimethylammonium,1-ethyl-3-methylimidazolium, 1-butyl-3-methylimidazolium,1-methyl-3-propylimidazolium, 1-hexyl-3-methylimidazolium, choline,ethylammonium, tributylmethylphosphonium,tributyl(tetradecyl)phosphonium, trihexyl(tetradecyl)phosphonium,1-ethyl-2,3-methylimidazolium, 1-butyl-1-methylpiperidinium,diethylmethylsulfonium , 1-methyl-3-propylimidazolium,1-methyl-l-propylpiperidinium, 1-butyl-2-methylpyridinium,1-butyl-4-methylpyridinium, 1-butyl-1-methylpyrrolidinium, and mixturesthereof.
 7. The composition of claim 1, wherein the first electrolytefurther comprises one or more ionic liquid anions selected from thegroup consisting of: tris(pentafluoroethyl)trifluorophosphate,trifluoromethanesulfonate, hexafluorophosphate, tetrafluoroborate, ethylsulfate, methyl sulfate, dimethyl phosphate, trifluoromethanesulfonate,methanesulfonate, triflate, tricyanomethanide, dibutylphosphate,bis(trifluoromethylsulfonyl)imide, bis-2,4,4-(trimethylpentyl)phosphinate, iodide, chloride, bromide, nitrate, thiocyanate, andmixtures thereof.
 8. The composition of claim 1, further comprising athird electrolyte different from the first and second electrolytes, thethird electrolyte comprising one or more electrolytes selected from thegroup consisting of: potassium hydroxide, sodium hydroxide, ammoniumhydroxide, lithium hydroxide, nickel hydroxide, cadmium hydroxide,magnesium hydroxide, sulfuric acid, hydrochloric acid, fluoroboric acid,ammonium chloride, zinc chloride, zincbis(trifluoromethanesulfonyl)imide, aluminium chloride, chromiumchloride, magnesium perchloride, barium chromate, lithium chromate,lithium-thyonyl chloride, lithiujm perchlorate, lithium bromide, lithiumtriflate, lithium hexafluorophosphate, lithium tetrafluoroborate,lithium bis-oxalato borate, lithium bis(trifluoromethanesulfonyl)imide,lithium bisoxalatoborate, lithium iodide, lithium tetrachloroaluminate,potassium carbonate, potassium fluoride, potassium borate, silvernitride, silver tetrafluoroborate; salts ofbis(trifluoromethylsulfonyl)imide,tris(pentafluoroethyl)trifluorophosphate, trifluoromethanesulfonate,hexafluorophosphate, tetrafluoroborate, ethyl sulfate, dimethylphosphate, trifluoromethanesulfonate, triflate, tricyanomethanide,dibutylphosphate; and mixtures thereof.
 9. A method of using thecomposition of claim 1, the method comprising: printing the compositionto form a liquid or gel separator.
 10. A method of fabricating a liquidor gel separator for separating and spacing apart at least twoconductors, the method comprising: depositing a composition over a firstconductor of the at least two conductors, the composition comprising: aplurality of particles; an ionic liquid as a first electrolyte, theionic liquid comprising 1-ethyl-3-methylimidazolium; a secondelectrolyte comprising zinc tetrafluoroborate salt, the first and secondelectrolytes present in an amount between 15 to 30 percent of the totalweight of the composition; and a polymer present in an amount between0.5 to 10 percent of the total weight of the composition and comprisingpolyvinyl alcohol (“PVA”) or polyvinylidene fluoride (“PVFD”).
 11. Themethod of claim 10, wherein the step of depositing comprises printingthe composition.
 12. The method of claim 10, wherein the compositionfurther comprises a solvent present in an amount between 10 to 30percent of the total weight of the composition, the solvent comprisingone or more solvents selected from the group consisting of: water;alcohols such as methanol, ethanol, N-propanol (including 1-propanol,2-propanol (isopropanol or IPA), 1-methoxy-2-propanol), butanol(including 1-butanol, 2-butanol (isobutanol)), pentanol (including1-pentanol, 2-pentanol, 3-pentanol), hexanol (including 1-hexanol,2-hexanol, 3-hexanol), octanol, N-octanol (including 1-octanol,2-octanol, 3-octanol), tetrahydrofurfuryl alcohol (THFA), cyclohexanol,cyclopentanol, terpineol; lactones such as butyl lactone; ethers such asmethyl ethyl ether, diethyl ether, ethyl propyl ether, and polyethers;ketones, including diketones and cyclic ketones, such as cyclohexanone,cyclopentanone, cycloheptanone, cyclooctanone, acetone, benzophenone,acetylacetone, acetophenone, cyclopropanone, isophorone, methyl ethylketone; esters such ethyl acetate, dimethyl adipate, proplyene glycolmonomethyl ether acetate, dimethyl glutarate, dimethyl succinate,glycerin acetate, carboxylates; glycols such as ethylene glycols,diethylene glycols, polyethylene glycols, propylene glycols, dipropyleneglycols, glycol ethers, glycol ether acetates; carbonates such aspropylene carbonate; glycerols and other polyols and polymeric polyolsor glycols such as glycerin, diol, triol, tetraol, pentaol, ethyleneglycol, 1,4-butanediol, 1,2-butanediol, 2,3-butanediol, 1,3-propanediol,1,4-butanediol, 1,5-pentanediol, 1,8-octanediol, 1,2-propanediol,1,3-butanediol, 1,2-pentanediol, etohexadiol, p-menthane-3,8-diol,2-methyl-2,4-pentanediol; tetramethyl urea, n-methylpyrrolidone,N-methyl-2-pyrrolidinone,acetonitrile, tetrahydrofuran (THF), dimethylformamide (DMF), N-methyl formamide (NMF), dimethyl sulfoxide (DMSO);thionyl chloride; sulfuryl chloride; and mixtures thereof.
 13. Themethod of claim 10, wherein the plurality of particles have a sizebetween 5 microns to 15 microns and are present in an amount between 40to 60 percent of the total weight of the composition, and wherein theplurality of particles comprise silicate glass or one or morediatomaceous particles or mixtures thereof.
 14. The method of claim 13,wherein the plurality of silicate glass particles are less than 10microns in any dimension.
 15. The method of claim 13, wherein theplurality of silicate glass particles have a size of 7 microns, plus orminus 2 microns, in any dimension.
 16. The method of claim 10, whereinthe plurality of particles are hollow.
 17. The method of claim 10,wherein the plurality of particles are selected from the groupconsisting of: diatoms, diatomaceous frustules, diatomaceous fragments,diatomaceous remains, and mixtures thereof.
 18. The method of claim 10,wherein the first electrolyte of the composition further comprises oneor more ionic liquid cations selected from the group consisting of:butyltrimethylammonium, 1-ethyl-3-methylimidazolium,1-butyl-3-methylimidazolium, 1-methyl-3-propylimidazolium,1-hexyl-3-methylimidazolium, choline, ethylammonium,tributylmethylphosphonium, tributyl(tetradecyl)phosphonium,trihexyl(tetradecyl)phosphonium, 1-ethyl-2,3-methylimidazolium,1-butyl-1-methylpiperidinium, diethylmethylsulfonium ,1-methyl-3-propylimidazolium, 1-methyl-l-propylpiperidinium,1-butyl-2-methylpyridinium, 1-butyl-4-methylpyridinium,1-butyl-1-methylpyrrolidinium, and mixtures thereof; and wherein thefirst electrolyte of the composition further comprises one or more ionicliquid anions selected from the group consisting of:tris(pentafluoroethyl)trifluorophosphate, trifluoromethanesulfonate,hexafluorophosphate, tetrafluoroborate, ethyl sulfate, methyl sulfate,dimethyl phosphate, trifluoromethanesulfonate, methanesulfonate,triflate, tricyanomethanide, dibutylphosphate,bis(trifluoromethylsulfonyl)imide, bis-2,4,4-(trimethylpentyl)phosphinate, iodide, chloride, bromide, nitrate, thiocyanate, andmixtures thereof.
 19. The method of claim 10, wherein the compositionfurther comprises a third electrolyte different from the first andsecond electrolytes, the third electrolyte comprising one or moreelectrolytes selected from the group consisting of: potassium hydroxide,sodium hydroxide, ammonium hydroxide, lithium hydroxide, nickelhydroxide, cadmium hydroxide, magnesium hydroxide, sulfuric acid,hydrochloric acid, fluoroboric acid, ammonium chloride, zinc chloride,zinc bis(trifluoromethanesulfonyl)imide, aluminium chloride, chromiumchloride, magnesium perchloride, barium chromate, lithium chromate,lithium-thyonyl chloride, lithiujm perchlorate, lithium bromide, lithiumtriflate, lithium hexafluorophosphate, lithium tetrafluoroborate,lithium bis-oxalato borate, lithium bis(trifluoromethanesulfonyl)imide,lithium bisoxalatoborate, lithium iodide, lithium tetrachloroaluminate,potassium carbonate, potassium fluoride, potassium borate, silvernitride, silver tetrafluoroborate; salts ofbis(trifluoromethylsulfonyl)imide,tris(pentafluoroethyl)trifluorophosphate, trifluoromethanesulfonate,hexafluorophosphate, tetrafluoroborate, ethyl sulfate, dimethylphosphate, trifluoromethanesulfonate, triflate, tricyanomethanide,dibutylphosphate; and mixtures thereof.
 20. A composition comprising: aplurality of particles having a size in any dimension between about 3.0to about 15 microns and present in an amount between 40 to 75 percent ofthe total weight of the composition, wherein the plurality of particlescomprise one or more particles selected from the group consisting of:silicate glass, silicon dioxide, alumina, polystyrene, melamine,diatoms, diatomaceous frustules, diatomaceous fragments; and mixturesthereof; an ionic liquid as a first electrolyte, the ionic liquidcomprising 1-ethyl-3-methylimidazolium; a second electrolyte differentfrom the first electrolyte, the second electrolyte comprises one or moreelectrolytes selected from the group consisting of: zinctetrafluoroborate, potassium hydroxide, sodium hydroxide, ammoniumhydroxide, lithium hydroxide, nickel hydroxide, cadmium hydroxide,magnesium hydroxide, sulfuric acid, hydrochloric acid, fluoroboric acid,ammonium chloride, zinc chloride, zincbis(trifluoromethanesulfonyl)imide, aluminium chloride, chromiumchloride, magnesium perchloride, barium chromate, lithium chromate,lithium-thyonyl chloride, lithium perchlorate, lithium bromide, lithiumtriflate, lithium hexafluorophosphate, lithium tetrafluoroborate,lithium bis-oxalato borate, lithium bis(trifluoromethanesulfonyl)imide,lithium bisoxalatoborate, lithium iodide, lithium tetrachloroaluminate,potassium carbonate, potassium fluoride, potassium borate, silvernitride, silver tetrafluoroborate; and mixtures thereof; a polymer orpolymeric precursor comprising polyvinyl alcohol (“PVA”) orpolyvinylidene fluoride (“PVFD”) or mixtures thereof; and a solventcomprising one or more solvents selected from the group consisting of:water; alcohols such as methanol, ethanol, N-propanol (including1-propanol, 2-propanol (isopropanol or IPA), 1-methoxy-2-propanol),butanol (including 1-butanol, 2-butanol (isobutanol)), pentanol(including 1-pentanol, 2-pentanol, 3-pentanol), hexanol (including1-hexanol, 2-hexanol, 3-hexanol), octanol, N-octanol (including1-octanol, 2-octanol, 3-octanol), tetrahydrofurfuryl alcohol (THFA),cyclohexanol, cyclopentanol, terpineol; lactones such as butyl lactone;ethers such as methyl ethyl ether, diethyl ether, ethyl propyl ether,and polyethers; ketones, including diketones and cyclic ketones, such ascyclohexanone, cyclopentanone, cycloheptanone, cyclooctanone, acetone,benzophenone, acetylacetone, acetophenone, cyclopropanone, isophorone,methyl ethyl ketone; esters such ethyl acetate, dimethyl adipate,proplyene glycol monomethyl ether acetate, dimethyl glutarate, dimethylsuccinate, glycerin acetate, carboxylates; glycols such as ethyleneglycols, diethylene glycols, polyethylene glycols, propylene glycols,dipropylene glycols, glycol ethers, glycol ether acetates; carbonatessuch as propylene carbonate; glycerols and other polyols and polymericpolyols or glycols such as glycerin, diol, triol, tetraol, pentaol,ethylene glycol, 1,4-butanediol, 1,2-butanediol, 2,3-butanediol,1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,8-octanediol,1,2-propanediol, 1,3-butanediol, 1,2-pentanediol, etohexadiol,p-menthane-3,8-diol, 2-methyl-2,4-pentanediol; tetramethyl urea,n-methylpyrrolidone, N-methyl-2-pyrrolidinone,acetonitrile,tetrahydrofuran (THF), dimethyl formamide (DMF), N-methyl formamide(NMF), dimethyl sulfoxide (DMSO); thionyl chloride; sulfuryl chloride;and mixtures thereof.